A Raman spectroscopic study on the structural disorder of monazite–(Ce)

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO₄ stretching near 970?cm^?1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν₁(PO₄) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.     

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

In this paper, possibilities and limits of the application of REE³⁺ luminescence (especially the Nd^{3+ 4}F_3/2 → ⁴I_9/2 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.     

Geophysical evidence of the Eastern Marginal Fault of the Cheb Basin (Czech Republic)

The western part of the Bohemian Massif hosts an intersection of two regional fault zones, the SW-NE trending Oh?e/Eger Graben and the NNW-SSE trending Mariánské Lázně Fault, which has been reactivated several times in the geological history and controlled the formation of the Tertiary Cheb Basin. The broader area of the Cheb Basin is also related to permanent seismic activity of M_L 3+ earthquake swarms. The Eastern Marginal Fault of the Cheb Basin (northern segment of the Mariánské Lázně Fault) separates the basin sediments and underlying granites in the SW from the Kru?né Hory/Erzgebirge Mts. crystalline unit in the NE. We describe a detailed geophysical survey targeted to locating the Eastern Marginal Fault and determining its geometry in the depth. The survey was conducted at the Kopanina site near the Nový Kostel focal zone, which shows the strongest seismic activity of the whole Western Bohemia earthquake swarm region. Complex geophysical survey included gravimetry, electrical resistivity tomography, audiomagnetotellurics and seismic refraction. We found that the rocks within the Eastern Marginal Fault show low resistivity, low seismic velocity and density, which indicates their deep fracturing, weathering and higher water content. The dip of the fault in shallow depths is about 60° towards SW. At greater depths, the slope turns to subvertical with dip angle of about 80°. Results of geoelectrical methods show blocky fabric of the Cheb Basin and deep weathering of the granite bedrock, which is consistent with geologic models based on borehole surveys.     

Effect of NAPL Source Morphology on Mass Transfer in the Vadose Zone

The generation of vapor‐phase contaminant plumes within the vadose zone is of interest for contaminated site management. Therefore, it is important to understand vapor sources such as non‐aqueous‐phase liquids (NAPLs) and processes that govern their volatilization. The distribution of NAPL, gas, and water phases within a source zone is expected to influence the rate of volatilization. However, the effect of this distribution morphology on volatilization has not been thoroughly quantified. Because field quantification of NAPL volatilization is often infeasible, a controlled laboratory experiment was conducted in a two‐dimensional tank (28 cm × 15.5 cm × 2.5 cm) with water‐wet sandy media and an emplaced trichloroethylene (TCE) source. The source was emplaced in two configurations to represent morphologies encountered in field settings: (1) NAPL pools directly exposed to the air phase and (2) NAPLs trapped in water‐saturated zones that were occluded from the air phase. Airflow was passed through the tank and effluent concentrations of TCE were quantified. Models were used to analyze results, which indicated that mass transfer from directly exposed NAPL was fast and controlled by advective‐dispersive‐diffusive transport in the gas phase. However, sources occluded by pore water showed strong rate limitations and slower effective mass transfer. This difference is explained by diffusional resistance within the aqueous phase. Results demonstrate that vapor generation rates from a NAPL source will be influenced by the soil water content distribution within the source. The implications of the NAPL morphology on volatilization in the context of a dynamic water table or climate are discussed.     

Evolution of nappes in the eastern margin of the Bohemian Massif: a kinematic interpretation

The entire pile of nappes in the eastern margin of the Bohemian massif is characterized by two stages of Variscan nappe emplacement each exhibiting a different kinematic and metamorphic evolution.The older emplacement (D1) probably occurred around 350-340 Ma ago and was synmetamorphic. The nappes show a typical systematic superposition of higher grade metamorphic units over lower grade ones. Thus, the crystalline complexes showing a HT-MP Barrovian imprint (Svratka allochthonous unit and Moldanubicum) were thrust over an intermediate unit affected by MTMP recrystallization (Bíte orthogneiss and its country rock), and at the base of the D1 nappe pile the Inner Phyllite Nappe (Biý Potok Unit) is characterized by LT/LP metamorphism.The second stage of tectonic evolution (D2) is characterized by a thin-skinned northward-oriented nappe emplacement that occurred under LT-LP conditions dated at 320-310 Ma. The whole nappe sequence formed during the first tectonometamorphic period (D1) was transported northward over the autochthonous »Deblín polymetamorphic and granitic complex« of Upper Proterozoic age and its Devonian sedimentary cover with very low metamorphism. During this second tectonic event the Brno granite massif (580 Ma) was only marginally incorporated in the Variscan nappe tectonics which resulted in kilometer-scale cover and basement duplexes. The tectonic evolution of the nappe pile ended with stage D3, represented by large- to medium-scale east-vergent folds with limited displacement.

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Zusammenfassung Der Deckenbau am Ostrand der Böhmischen Masse erfolgte in zwei aufeinanderfolgenden Stadien, die sich sowohl in ihrer Kinematik als auch in ihrer Metamorphoseentwicklung deutlich voneinander unterschieden.Die ältere Phase (D1 ca. 350-340 Ma) ist durch synmetamorphe Überschiebungen charakterisiert. Sie führt zu einer metamorphen Inversion der überschobenen Deckeneinheiten, so daß generell hohe metamorphe Einheiten schwach metamorphe tektonisch überlagern. Der Svratka Komplex und das Moldanubikum als hangendste Decken sind durch MP/HT Paragenesen vom Barrow-Typ gekennzeichnet. Beide Einheiten sind auf den MP/MT-metamorphen Bite-Gneis und seine Rahmengesteine überschoben. Die Bílý potok Einheit als liegende Decke zeigt nur noch eine LP/ LT Regionalmetamorphose.Das jüngere Stadium (D2 ca. 320-310 Ma) ist durch eine Thin-skinned Tektonik mit nordvergentem Deckentransport unter LP/LT Bedingungen charakterisiert. Der gesamte, invers metamorphe D1-Deckenstapel wird dabei nach N über den autochtonen Deblín Komplex bzw. seine devonische Sedimenthülle überschoben.Das Brno Granit Massiv (580 Ma) wird nur randlich in diesen variszischen Deckenbau einbezogen. Die tektonische Entwicklung endet mit einem mittel bis großräumigen E-vergenten Faltenbau (D3 phase).

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Résumé L'empilement des nappes a la bordure orientale du Massif de Bohème est caractérisé par deux stades de mise en place présentant différentes évolutions cinématiques et métamorphiques.La tectonique majeure de mise en place des nappes crustales intervient lors d'un métamorphisme de type barrowien, calé autour de 350-340 Ma. L'empilement qui en résulte montre une superposition systématique d'unités à fort degré de métamorphisme sur des unités moins métamorphiques. Ainsi les complexes cristallins, montrant des reliques de métamorphisme de haute à moyenne pression-haute température (unités cristallines de Svratka et du Moldanubien), chevauchent une unité intermédiaire affectée par un métamorphisme de moyenne à basse pression-moyenne température (l'orthogneiss de Bíte et son encaissant). A la base de cette pile édifiée durant la tectonique D1, l'unité des phyllites internes (unité de Bílý potok) est caractérisée par un métamorphisme de basse témperature-basse pression.Le second stade D2 de l'évolution tectonique est caractérisé par une tectonique pelliculaire à vergence nord datée à 320-310 Ma. L'empilement résultant de D1 est ainsi transporté vers le nord, au dessus du complexe autochtone d'âge protérozoïque supérieur (groupe de Deblín) et sa couverture sédimentaire dévonienne très faiblement métamorphisée.Le massif granitique de Brno (580 Ma) n'est que marginalement incorporé à cette tectonique de nappe varisque. Ceci se traduit par des duplex socle-couverture d'échelle plurikilométrique. L'évolution tectonique s'achève lors d'une troisième phase, marquée par de grands plis à vergence est. Le déplacement associé est alors d'amplitude limitée.

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Nb-Ta-Ti oxides fractionation in rare-metal granites: Kr��sno-Horn�� Slavkov ore district, Czech Republic

Nb-Ta-Ti-bearing oxide minerals (Nb-Ta-bearing rutile, columbite-group minerals) represent the most common Nb-Ta host in topaz-albite granites and related rocks from the Krásno-Horní Slavkov ore district. Tungsten-bearing columbite-(Fe), W-bearing ixiolite, wodginite and tapiolite-(Fe) are extremely rare in these rocks. Rutile contains significant levels of Ta (up to 37?wt.% Ta₂O₅) and Nb (up to 24?wt.% Nb₂O₅), with Ta/(Ta?+?Nb) ratio ranging from 0.04 to 0.61. Columbite-group minerals are represented mostly by columbite-(Fe) and rarely by columbite-(Mn), with Mn/(Mn?+?Fe) ratio ranging from 0.23 to 0.94. The exceptionally rare Fe-rich, W-bearing ixiolite occurs only as inclusions in Nb-Ta-bearing rutile from quartz-free alkali-feldspar syenites (Vysoky Kámen stock). Wodginite was found only in the topaz-albite microgranite of gneissic breccia matrix that occurs in the upper most part of the Hub topaz-albite granite stock. In wodginite, the Mn/(Mn?+?Fe) ratio is 0.42?C0.51, whereas the coexisting tapiolite-(Fe) has a distinctly lower Mn/(Mn?+?Fe) ratio close to 0.06.     

Magnetic particles in atmospheric particulate matter collected at sites with different level of air pollution

Magnetic measurements of deposited atmospehric dust can serve as an additional parameter in assessing environmental pollution. This method is based on the assumption that atmospherically deposited particles contain significant portion of ferrimagnetic iron oxides of anthropogenic origin, which can be easily detected. Aim of this paper is to identify clearly magnetic fraction of daily samples of particulate matter less than 10 μm (PM10), routinely used for air quality assessment and monitoring. We used combination of thermomagnetic analyses and other physical and chemical methods, including scanning electron microscopy (SEM) and Mössbauer spectroscopy. Our results show that daily samples of PM10, collected at sites with different degree of atmospheric pollution, contain magnetite of spherical shape, which is presumably of industrial origin. Thus, magnetic methods can be applied directly to the same substances, which are used routinely in air quality assessment and monitoring.     

Zircon and whole-rock Zr/Hf ratios as markers of the evolution of granitic magmas: Examples from the Teplice caldera (Czech Republic/Germany)

Mineralogy and Petrology - Hafnium contents and Zr/Hf ratios were studied in zircons and their parent rocks from three magmatic suites associated with the Teplice caldera, Eastern Erzgebirge:...     

Combined tectonic-sediment supply-driven cycles in a Lower Carboniferous deep-marine foreland basin,Moravice Formation,Czech Republic

The Lower Carboniferous Moravian–Silesian Culm Basin (MSCB) represents the easternmost part of the Rhenohercynian system of collision-related, deep-water foreland basins (Culm facies). The Upper Viséan Moravice Formation (MF) of the MSCB shows a distinct cyclic stratigraphic arrangement. Two major asymmetric megacycles bounded by basal sequence boundary, each about 500 to 900 m thick, have been revealed. The megacycles start with 50- to 250-m-thick, basal segments of erosive channels: overbank successions and slope apron deposits interpreted as lowstand turbidite systems. Up-section they pass into hundred metre-thick, fine-grained, low-efficiency turbidite systems. Palaeocurrent data show two prominent directions, basin axis-parallel, SSW–NNE directions, which are abundant in the whole MF, and basin axis-perpendicular to oblique, W–E to NW–SE directions, which tend to be confined to the basal parts of the megacycles or channel-lobe transition systems in their upper parts. Based on the facies characteristics, palaeocurrent data, sandstone composition data and trace-fossil distribution data, we suggest a combined tectonics–sediment supply-driven model for the MF basin fill. Periods of increased tectonic activity resulted in slope oversteepening probably combined with increased rate of lateral W–E sediment supply into the basin, producing the basal sequence boundary and the subsequent lowstand turbidite systems. During subsequent periods of tectonic quiescence, the system was filled mainly from a distant southern point source, producing the thick, low efficiency turbidite systems. Consistently with the previous models, our own sediment composition data indicate a progressively increasing sediment input from high-grade metamorphic and magmatic sources up-section, most probably related to an uplift in the source area and progressive unroofing of its structurally deeper crustal parts. The first occurrence of the Cruziana–Nereites ichnofacies in sand-rich turbidite systems in the youngest parts of the MF (Goel to Gospi Zone), supported by rapidly increasing quartz concentrations in sandstones, is thought to indicate a transition from generally underfilled to generally overfilled phase in evolution of the MSCB basin. This transition may be linked to the onset of Upper Viséan phase of northward basin-fill progradation assumed by previous authors.     

Spectroscopic and bond-topological investigation of interstitial volatiles in beryl from Slovakia

Nine beryl samples from Western Carpathians, Slovakia, were investigated by infrared and Raman spectroscopy and differential thermal analysis. Two types of water H₂O I and H₂O II were detected. Infrared spectroscopy proved the presence of water type I and II in the presence of alkali cations with several bands: (1) symmetric stretching vibration—ν₁; (2) antisymmetric stretching mode—ν₃; (3) bending vibration—ν₂. The presence of singly and doubly coordinated type II water (IIs and IId) was confirmed by single-crystal IR spectroscopy. From Raman spectra a band at 3606 cm^?1 was assigned to ν₁ of water type I and the range of 3597–3600 cm^?1 to water type II. The presence of doubly coordinating water indicates a relatively highly hydrated environment with the presence of alkali ions including Na as the dominant cation coordinated by H₂O II. CO₂ bands were detected only by single-crystal IR spectroscopy. Thermal analysis proved total water loss in the range of 1.4–2.0 wt% and three main dehydration events. Based on the study of bond-topological arrangements two molecules of H₂O IId are each bound with two H···O1 bonds and one Na–O_W bond with an angular distortion, and by releasing one H₂O molecule more stable H₂O IIs is produced. The H₂O I molecule is bound only by two equivalent hydrogen bonds. The H₂O IIs molecule with a Na–O_W bond strength of 0.28 vu and two H···O1 bonds of 0.14 vu without any forced angular distortion is the most stable of all.