Dominik Talla

Factors affecting the Nd3+ (REE3+) luminescence of minerals

In this paper, possibilities and limits of the application of REE3+ luminescence (especially the Nd3+4F3/2 → 4I9/2 emission) as structural probe are evaluated. Important factors controlling the Nd3+ luminescence signal are discussed, including effects of the crystal-field, crystal orientation, structural state, and temperature. Particular attention was paid to the study of the accessory minerals zircon (ZrSiO4), xenotime–(Y) (YPO4), monazite–(Ce) (CePO4) and their synthetic analogues. Based on these examples we review in short that (1) REE3+ luminescence can be used as non-destructive phase identification method, (2) the intensities of certain luminescence bands are strongly influenced by crystal orientation effects, and (3) increased widths of REE3+-related emission bands are a strong indicator for structural disorder. We discuss the potential of luminescence spectroscopy, complementary to Raman spectroscopy, for the quantitative estimation of chemical (and potentially also radiation-induced) disorder. For the latter, emissions of Nd3+-related centres are found to be promising candidates.

On the presence of OH defects in the zircon-type phosphate mineral xenotime, (Y,REE)PO4

Abstract The infrared (IR) spectra of gem-quality xenotime crystals containing considerable amounts of rare earth elements (REEs), are characterized by sharp and strongly pleochroic absorption bands in the 3650-3350 cm-1 region. In contrast, the spectra of partially metamict samples are dominated by a broad band centered at around 3450 cm-1. Xenotime presents the interesting case of a nominally anhydrous mineral, where the OH stretching frequency region of weakly hydrogen-bonded OH groups is overlapped by absorption bands due to low-energetic f-f electron transitions of REEs, especially of dysprosium. In polarized spectra measured parallel to the c-axis, Dy shows a prominent sharp band at 3519 cm-1. The assignment of the REE bands is based on the polarized IR spectra of REE doped xenotime single crystals, which have been synthesized by the flux method. A single band at 3480 cm-1, strongly polarized perpendicular to the c-axis, is assigned to the stretching vibration of an OH group. Deuteration experiments performed at 950 °C prove the assignment of this band and the presence of additional structural OH groups, appearing at annealing temperatures above 500 °C. Models of the OH point defect incorporation into the crystal structure of xenotime can be derived on the basis of fully occupied cation sites and under the assumption of Y- and P-site vacancies. The water content of the gem-quality samples ranges from 5 to 10 wt ppm and for the partially metamict samples from 370 wt ppm to 1.7 wt% H2O.

Běhounekite, U(SO4)2(H2O)4, from Jáchymov (St Joachimsthal),Czech Republic: the first natural U4+ sulphate.

Abstract Běhounekite, orthorhombic U(SO4)2(H2O)4, is the first natural sulphate of U4+. It was found in the Geschieber vein, Jáchymov (St Joachimsthal) ore district, Western Bohemia, Czech Republic, crystallized on the altered surface of arsenic and associated with kaatialaite, arsenolite, claudetite, unnamed phase UM1997-20-AsO:HU and gypsum. Běhounekite most commonly forms short-prismatic to tabular green crystals, rarely up to 0.5 mm long. The crystals have a strong vitreous lustre and a grey to greenish grey streak. They are brittle with an uneven fracture and have very good cleavage along {100}. The Mohs hardness is about 2. The mineral is not fluorescent either in short- or long-wavelength UV radiation. Běhounekite is moderately pleochroic, α∼β is pale emerald green and γ is emerald green, and is optically biaxial (+) with α = 1.590(2), β = 1.618(4), γ = 1.659(2) (590 nm), 2V (calc.) = 81º, birefringence 0.069. The empirical formula of Běhounekite (based on 12 O atoms, from an average of five point analyses) is (U0.99Y0.03)Σ1.02(SO4)1.97(H2O)4. The simplified formula is U(SO4)2(H2O)4, which requires UO2 53.77, SO331.88, H2O 14.35, total 100.00 wt.%. Běhounekite is orthorhombic, space group Pnma, a = 14.6464(3), b = 11.0786(3), c = 5.6910(14) Å, V = 923.43(4) Å3, Z = 4, Dcalc = 3.62 g cm-3. The seven strongest diffraction peaks in the X-ray powder diffraction pattern are [dobs in Å (I) (hkl)]: 7.330 (100) (200), 6.112 (54) (210), 5.538 (21) (020), 4.787 (42) (111), 3.663 (17) (400), 3.478 (20) (410), 3.080 (41) (321). The crystal structure of běhounekite has been solved by the charge-flipping method from singlecrystal X-ray diffraction data and refined to R 1 = 2.10 % with a GOF = 1.51, based on 912 unique observed diffractions. The crystal structure consists of layers built up from [8]-coordinate uranium atoms and sulphate tetrahedra. The eight ligands include four oxygen atoms from the sulphate groups and four oxygen atoms from the H2O molecules. Each uranium coordination polyhedron is connected via sulphate tetrahedra with other uranium polyhedra and through hydrogen bonds to the apices of sulphate tetrahedra. The dominant features of the Raman and infrared spectra of běhounekite are related to stretching vibrations of SO4 tetrahedra (~1200-950 cm1), O-H stretching modes (~3400-3000 cm1) and H-O-H bending modes (~1650 cm1). The mineral is named in honour of Frantisěk Běhounekite, a well known Czech nuclear physicist.

Compositional evolution of grossular garnet from leucotonalitic pegmatite at Ruda nad Moravou, Czech Republic; a complex EMPA, LA-ICP-MS, IR and CL study

Five distinct paragenetic, morphological and compositional types of grossular garnet (G1, G2, G3, G4, G5) were distinguished within the individual (sub)units of the zoned leucotonalitic pegmatite cutting serpentinized lherzolite with rodingite dikes at Žďár near Ruda nad Moravou, Staré Město Unit, Northern Moravia. Detailed study using Electron Microprobe Analysis, Laser Ablation Inductively Coupled Plasma Mass Spectrometry, Cathodoluminiscence and Infrared Spectroscopy revealed distinct compositional trends in major, minor and trace elements. The contents of Fe3+, Mn, Mg and Ti increase from early garnet (G1) in the outermost grossular subunit through the interstitial garnet (G2) in the leucocratic subunit to graphic intergrowths of quartz+garnet (G3) in the coarse-grained unit. Then these constituents decrease in inclusions of garnet (G4) from the blocky unit and large crystals of garnet (G5) from the quartz core. Some trace elements (V, Ni, Y) exhibit the same trends, only Be evidently increases in garnet from border zone to the centre. Fluorine has negative correlation with Fe3+ as well as some trace elements (Ta, Pb). Concentrations of H2O in garnets, up to 0.22 wt.% H2O, are comparable with spessartine-almandine garnets from the Rutherford No. 2 pegmatite, Virginia, and grossular garnets from high-temperature calc-silicate rocks (skarns). Water contents correlate positively with Fe3+, but inversely with F. The use of water contents in garnet to elucidate the fluctuations of activity of H2O during the pegmatite formation is only limited; the incorporation of hydrous defects seems to be controlled instead by crystal-structural constraints. However, the sum of all volatile components (H2O + F) increases about twice from the outermost subunit to the centre of the pegmatite body.

Polarized FTIR spectroscopic examination on hydroxylation in the minerals of the wolframite group, (Fe,Mn,Mg)[W,(Nb,Ta)][O,(OH)] 4

Abstract Polarized FTIR spectroscopic measurements of 11 natural wolframite single crystals from different occurrences revealed the common presence of structurally bound OH groups in their crystal lattice, with potential influence on the properties of thisse geologically and technologically important group of compounds. Despite differences in the appearance of the OH absorption pattern, dependent among other on the end-member ratio, two types of “intrinsic” OH defects could be discerned from detailed studies of the pleochroic behavior of the absorption bands both at 80 K and room temperature. The accompanying chemical analyses by the electron microprobe helped to clearly identify the substitution trend W6+ + O2– ↔ (Nb,Ta)5+ + OH– as the prevailing hydrogen incorporation mechanism into wolframite. The assignment of the observed IR absorption phenomena to hydrous defects was confirmed by the results of deuteration experiments and the negligible contribution of included impurities to the FTIR spectra in the OH absorption region. The results obtained in this study of natural wolframite crystals can be used to detect and analyze hydrous defects in synthetic technologically important tungstates.