Magma hybridization in the Western Tatra Mts. granitoid intrusion (S-Poland, Western Carpathians)
In the Variscan Western Tatra granites hybridization phenomena such as mixing and mingling can be observed at the contact of mafic precursors of dioritic composition and more felsic granitic host rocks. The textural evidence of hybridization include: plagioclase-K-feldspar-sphene ocelli, hornblende- and biotite-rimmed quartz ocelli, plagioclase with Ca-rich spike zonation, inversely zoned K-feldspar crystals, mafic clots, poikilitic plagioclase and quartz crystals, mixed apatite morphologies, zoned K-feldspar phenocrysts. The apparent pressure range of the magma hybridization event was calculated at 6.1 kbar to 4.6 kbar, while the temperature, calculated by independent methods, is in the range of 810°C-770°C. U-Pb age data of the hybrid rocks were obtained by in-situ LA-MC-ICP-MS analysis of zircon. The oscillatory zoned zircon crystals yield a concordia age of 368 ± 8 Ma (MSWD = 1.1), interpreted as the age of magma hybridization and timing of formation of the magmatic precursors. It is the oldest Variscan magmatic event in that part of the Tatra Mountains.
Pre-Variscan evolution of the Western Tatra Mountains: new insights from U-Pb zircon dating
In situ LA-MC-ICP-MS U-Pb zircon geochronology combined with cathodoluminescence imaging were carried out to determine protolith and metamorphic ages of orthogneisses from the Western Tatra Mountains (Central Western Carpathians). The metamorphic complex is subdivided into two units (the Lower Unit and the Upper Unit). Orthogneisses of the Lower Unit are mostly banded, fine- to medium-grained rocks while in the Upper Unit varieties with augen structures predominate. Orthogneisses show a dynamically recrystallised mineral assemblage of Qz + Pl + Bt ± Grt with accessory zircon and apatite. They are peraluminous (ASI = 1.20-1.27) and interpreted to belong to a high-K calc-alkaline suite of a VAG-type tectonic setting. LA-MC-ICP-MS U-Pb zircon data from samples from both units, from crystals with oscillatory zoning and Th/U > 0.1, yield similar concordia ages of ca. 534 Ma. This is interpreted to reflect the magmatic crystallization age of igneous precursors. These oldest meta-magmatics so far dated in the Western Tatra Mountains could be linked to the fragmentation of the northern margin of Gondwana. In zircons from a gneiss from the Upper Unit, cores with well-developed oscillatory zoning are surrounded by weakly luminescent, low contrast rims (Th/U < 0.1). These yield a concordia age of ca. 387 Ma corresponding to a subsequent, Eo-Variscan, high-grade metamorphic event, connected with the formation of crustal-scale nappe structures and collision-related magmatism.
Factors affecting the Nd (REE) luminescence of minerals
In this paper, possibilities and limits of the application of REE luminescence (especially the NdF → I emission) as structural probe are evaluated. Important factors controlling the Nd 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 (ZrSiO), xenotime-(Y) (YPO), monazite-(Ce) (CePO) and their synthetic analogues. Based on these examples we review in short that (1) REE 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 REE-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 Nd-related centres are found to be promising candidates.
Cu- and Mn-bearing tourmalines from Brazil and Mozambique: crystal structures, chemistry and correlations
Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <-O> distances and the (Li + Mn + Cu + Fe) content (apfu) at this site with = 0.90. An excellent negative correlation exists between the <-O> distances and the AlO content ( = 0.94). The samples at each locality generally show a strong negative correlation between the -site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.
Structural investigations of the two polymorphs of synthetic Fe-cordierite and Raman spectroscopy of hexagonal Fe-cordierite
The crystal structures of synthetic hexagonal and orthorhombic Fe-cordierite polymorphs with the space groups 6/ and were refined from single-crystal ray diffraction data to = 3.14 % and = 4.48 %. The substitution of the larger Fe for Mg leads to multiple structural changes and an increase of the unit cell volumes, with , (hex) = 9.8801(16) Å, 9.2852(5) Å and , , (ortho) = 17.2306(2) Å, 9.8239(1) Å, 9.2892(1) Å in the end-members. Furthermore Fe incorporation results in an increase of the volumes of the octahedra, although the diameters of the octahedra in direction of the -axis decrease in both polymorphs. X-ray powder diffraction analysis indicates a high degree of Al/Si ordering in the orthorhombic polymorph, the Miyashiro distortion index is ~0.24. Estimations of site occupancies based on the determined tetrahedral volumes result in the following values for hexagonal Fe-cordierite: ~73 % Al for T and ~28 % Al for T. For the first time Raman spectroscopy was performed on the hexagonal Fe-cordierite polymorph. In the hexagonal Fe-cordierite polymorph most Raman peaks are shifted towards lower wavenumbers when compared with the Mg-end-member.
Attrition in the kimberlite system
The sustained transportation of particles in a suspension commonly results in leading to grain size reduction and shape modification. Particle attrition is a well-studied phenomenon that has mainly focussed on sediments produced in aeolian or fluvial environments. Here, we present analogue experiments designed to explore processes of attrition in the kimberlite system; we focus on olivine as it is the most abundant constituent of kimberlite. The attrition experiments on olivine use separate experimental set-ups to approximate two natural environments relevant to kimberlites. Tumbling mill experiments feature a low energy system supporting near continual particle-particle contact and are relevant to re-sedimentation and dispersal processes. Experiments performed in a fluidized particle bed constitute a substantially higher energy environment pertinent to kimberlite ascent and eruption. The run-products of each experiment are analysed for grain size reduction and shape modification and these data are used to elucidate the rates and extents of olivine attrition as a function of time and energy. Lastly, we model the two experimental datasets with an empirical rate equation that describes the production of daughter products (fines) with time. Both datasets approach a fines production limit, or plateau, at long particle residence times; the fluidized system is much more efficient producing a substantially higher fines content and reaches the plateau faster. Our experimental results and models provide a way to forensically examine a wide range of processes relevant to kimberlite on the basis of olivine size and shape properties.
The parisite-(Ce) enigma: challenges in the identification of fluorcarbonate minerals
A multi-methodological study was conducted in order to provide further insight into the structural and compositional complexity of rare earth element (REE) fluorcarbonates, with particular attention to their correct assignment to a mineral species. Polycrystals from La Pita Mine, Municipality de Maripí, Boyacá Department, Colombia, show syntaxic intergrowth of parisite-(Ce) with röntgenite-(Ce) and a phase which is assigned to (i.e., bastnäsite-3-synchisite-4; still unnamed) fluorcarbonate. Transmission electron microscope (TEM) images reveal well-ordered stacking patterns of two monoclinic polytypes of parisite-(Ce) as well as heavily disordered layer sequences with varying lattice fringe spacings. The crystal structure refinement from single crystal X-ray diffraction data - impeded by twinning, complex stacking patterns, sequential and compositional faults - indicates that the dominant parisite-(Ce) polytype has space group . Parisite-(Ce), the phase and röntgenite-(Ce) show different BSE intensities from high to low. Raman spectroscopic analyses of parisite-(Ce), the phase and röntgenite-(Ce) reveal different intensity ratios of the three symmetric CO stretching bands at around 1100 cm. We propose to non-destructively differentiate parisite-(Ce) and röntgenite-(Ce) by their 1092 cm / 1081 cm ν(CO) band height ratio.
The use of geochemical methods to pinpoint the origin of ancient white marbles
"Multi-method-approach" has now been for many years the buzzword in marble provenance analysis. Nevertheless a true combination of the results of different analytical methods is rarely applied in the sense of the combined simultaneous use of a large number of analytically obtained numerical variables. It is demonstrated here that the combination of data from isotope analysis, chemical data, and data from the chemical analysis of inclusion fluids of an artefact and of course in combination with a corresponding database enhances substantially the accuracy of marble provenance analysis. It is explicitly pointed out that the unchallenged collection of data of the chemical composition of marbles from different sources (and different analytical procedures) most probably implies severe differences in their comparability. Exemplarily presented is the nearly perfect discrimination of the most important fine-grained marbles and furthermore the possibility of the intra-site discrimination of the three Carrara districts and the assignment of two portrait heads to the Carrara Torano quarries.
Are the [6]-coordinated sites in tourmaline in certain cases partially vacant?
Tourmaline has two different [6]-coordinated sites, the Y site and the Z site. Vacancies were reported from both sites. Based on high-quality chemical and single-crystal structural data it usually needs increasing proportions of short-range order configurations Na(Al)Al(BO)[SiO](OH)(OH) or Na(Al)Al(BO)[SiO](OH)F in order to produce Y-site vacancies (with being the symbol for a vacant site). Less commonly, the short-range configuration Ca(Al)Al(BO)[SiTO](OH)(OH) could occur in Al-rich tourmalines with a Si deficiency, where T = B, Al. Therefore, tourmalines enriched in cations with charge 2 + (Fe, Mn, Mg) contain only insignificant Y-site vacancies. Aluminum-rich tourmalines with ≥ 7.0 apfu Al that usually contain ≥ 0.2 apfu Li may have significant vacancies at the Y site. However, no more than 12% vacancies (0.36 pfu) at the Y site can be observed in such samples. If no chemical data for Li is available it is proposed to calculate the Li content in such colourless or coloured tourmalines (elbaite, fluor-elbaite, fluor-liddicoatite, rossmanite) for Y = 2.8 apfu or for Y + Z + T = 14.8 apfu, because this calculation should give more accurate results than calculating the Li content as the difference to 3.0 apfu at the Y site. For Fe-rich and Mg-bearing tourmalines from the schorl-dravite series with MgO > 1.0 wt% (and only minor amounts of Fe, Cr and V) the structural formula can still be calculated for Y + Z + T = 15 apfu, because such tourmalines do not appear to contain significant Y-site vacancies. It can further be concluded that the Z site could be only ≤ 1% vacant and therefore such vacancies would be insignificant even in Al-rich tourmaline.