Geochemistry of highly saline fluids in siliciclastic sequences: genetic implications for post-Variscan fluid flow in the Moravosilesian Palaeozoic of the Czech Republic

Ubiquitous post-Variscan dolomites occur in Zn–Pb–Cu veins at the Nízký Jeseník Mountains and the Upper Silesian Basin (Lower and Upper Carboniferous siliciclastics at the eastern part of the Bohemian Massif). Crush–leach, stable isotope (oxygen and carbon) and microthermometry analysis of the fluid inclusions in dolomites enable understanding the geochemistry, origin and possible migration pathways of the fluids. Homogenisation temperatures of fluid inclusions range between 66 and 148°C, with generally higher temperatures in the Nízký Jeseník Mountains area than in the Upper Silesian Basin. The highest homogenisation temperatures (up to 148°C) have been found near major regional faults and the lowest in a distant position or at higher stratigraphic levels. Highly saline (16.6–28.4 eq. wt% NaCl) H₂O–NaCl–CaCl₂ ± MgCl₂ fluids occur in inclusions. Na–Cl–Br systematics of trapped fluids and a calculated oxygen isotopic fluid composition between ?0.9 and +3.0‰ V-SMOW indicate that the fluid was derived from evaporated seawater. Stable isotopic modelling has been used to explain stable isotopic trends. Isotopic values (δ¹³C = ?6.0/+2.0‰ V-PDB, δ¹⁸O = +15.5/+22.5‰ V-SMOW of dolomites) resulted from fractionation and crystallisation within an open system at temperatures between 80 and 160°C. Rock-buffering explains the isotopic composition at low w/r ratios. Organic matter maturation caused the presence of isotopically light carbon in the fluids and fluid–rock interactions largely controlled the fluid chemistry (K, Li, Br and Na contents, K/Cl, I/Cl and Li/Cl molar ratios). The fluid chemistry reflects well the interaction between the fluid and underlying limestones as well as with clay- and organic-rich siliciclastics. No regional trends in temperature or fluid geochemistry favour a fluid migration model characterised by an important vertical upward migration along major faults. A permeable basement and fractured sedimentary sequence enhanced the general nature of the fluid system. Fluid characteristics are comparable with the main post-Variscan fluid flow systems in the Polish (Cracow-Silesian ore district) and German sedimentary basins.     

Calculated trends of oh infrared stretching vibrations with composition and structure in aluminosilicate molecules

Ab initio, molecular orbital calculations have been performed on a variety of hypothetical aluminosilicate molecules to investigate relationships among composition, structure, and infrared spectra of OH. Vibrational analyses of the full-optimized molecular geometries at the 3–21G^** level were performed with Gaussian 92 to determine theoretical infrared spectra. Theoretical infrared OH frequencies, ν(OH), shift 10 to 100 cm^?1 with ionic substitutions. The inverse correlation of theoretical infrared OH intensities with OH stretching frequencies in these aluminosilicate molecules is similar to that observed for aluminosilicate glasses (Paterson 1982). O-H bond lengths, H-bond distances, and H?nd angles correlate with frequency. The dominant factor affecting ν(OH) is the H-bond distance, if this distance is less than 2 Å. Beyond H-bond distances of 2 Å, structural and compositional effects exert competitive influences on ν(OH).     

Tensional crack development in physical models with inhomogeneities under load

Summary The paper deals with a study of the mean stress field (_M) and its gradient (_M/x) in uniaxially loaded two-dimensional models of small thickness with respect to other dimensions, in which two inhomogeneities, e.g., a circular opening and a linear slit have been made. Particular attention was paid to the stress field development in the treated models durin gthe change of the mutual geometric configuration of both the inhomogeneities in question. The problem was analysed theoretically by means of Muskhelishvili's potentials of the two-dimensional theory of elasticity. To compare the results of calculations, the schlieren method was used to visualize and record the studied gradients of stress fields in physical models. The results of the calculations were calibrated by laboratory tests. In this way the individual model situations were classified from the point of view of their resistance to the applied load.     

Geochemical facies model of ore formation in the Grythyttan-Hällefors area,Bergslagen, Central Sweden

The different iron and manganese ore deposits of the Grythyttan-Hällefors area display an arrangement that reflects a systematic change in redox conditions from oxidic banded iron formation into highly reduced graphite-bearing slates. This phenomenon is explained by a facies model. The different environmental conditions are also held to be responsible for the geochemical differentiation of base metal deposits into Cu ores associated with minerals of Bi, Co, Mo, As, Zn, Pb, Au, and Pb-Zn-Ag ores associated with minerals of Sb, Mn, As, Sn, Cu. Spatial relationships between deposits of these two groups and certain iron and manganese deposits point to a common source of all metals, possibly connected with exhalative derivates from basic volcanism.

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Zusammenfassung Die verschiedenen Eisen- und Manganerz-Bildungen des Grythyttan-Hällefors-Gebietes zeigen Verhältnisse auf, die einem systematischen Wechsel der Redoxbedingungen wiedergeben, von oxidischer Bändereisenerzbildung bis hin zu stark reduzierten graphitführenden Schiefern. Dieses Phänomen wird durch ein Fazies-Modell erklärt. Die unterschiedlichen Milieu-Bedingungen werden auch als Ursache für die geochemische Diferentiation unedler Metall-Ablagerungen in Cu-Erze angesehen, die mit Mineralien assoziiert sind, die Bi, Co, Mo, As, Zn, Pb, Au führen und in Pb-Zn-Ag-Erze in Verbindung mit Sb-, Mn-, As-, Sn- und Cu-führenden Mineralien. Die räumlichen Beziehungen zwischen Ablagerungen dieser zwei Gruppen und gewissen Eisen- und Mangan-Bildungen weisen auf eine gemeinsame Quelle aller Metalle hin, die möglicherweise mit exhalativen Derivaten eines basischen Vulkanismus in Verbindung steht.

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Résumé Les différents gisements de minerais de Fe et Mn de la région de Grythyttan-Hällefors montrent une disposition qui réflète un changement systématique dans les ernolitions de réduction des formations rubanées de fer oxydé en phyllades graphiteux. Ce phénomène s'explique suivant un modèle faciétal. Les différentes conditions de l'environnement sont ainsi rendues responsables de la différentiation géochimique des gisements métallifères de base en minerais de Cu associés à des minéraux de Bi, Co, Mo, As, Zn, Pb, Au et des minerais de Pb-Zn-Ag associés à des minéraux de Sb, Mn, As, Sn, Cu. Des relations spatiales entre les gisements de ces deux groupes et certains gisements de Fe et Mn indiquent une source commune pour tous les métaux, en liaison possible avec des émanations du volcanisme basique.

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ATR-FTIR spectroscopic characterization of coexisting carbonate surface complexes on hematite

The speciation of carbonate adsorbed to hematite in air-equilibrated aqueous solutions has been studied using ATR-FTIR spectroscopy. Samples were measured over a range of pH conditions, at 0.1 M NaCl and at low ionic strength, and in H₂O and D₂O solutions to permit a multispecies analysis of the data. Second-derivative analyses and fits to the spectra indicate the presence of two major and two minor surface-bound carbonate species. The two major complexes coexist at near-neutral pH and low ionic strength. One of these two complexes is relatively sensitive to ionic strength, being displaced at 0.1 M NaCl, whereas the other is not. Comparison of experimental to DFT/MO-calculated frequencies suggest these two major species to be (a) a monodentate binuclear inner-sphere carbonate surface complex, and (b) a fully or partially solvated carbonate (CO₃²⁻) species that is symmetry broken and appears to reside in the structured vicinal water layers at the hematite-water interface, retained by hydrogen bonding and/or other forces. Minor carbonate complexes include diffuse layer CO₃²⁻ and an unidentified inner-sphere species. Both of the dominant species observed here are likely to be significant controls of the surface charge and sorptive properties of Fe-oxides.     

Magnetic activity and evolution of Algol-type stars – II

We examine the possibility of probing dynamo action in mass-losing stars, components of Algol-type binaries. Our analysis is based on the calculation of non-conservative evolution of these systems. We model the systems U Sge and β Per where the more massive companion fills its Roche lobe at the main sequence (case AB) and where it has a small helium core (early case B) respectively. We show that to maintain evolution of these systems at the late stages which are presumably driven by stellar 'magnetic braking', an efficient mechanism for producing large-scale surface magnetic fields in the donor star is needed. We discuss the relevance of dynamo operation in the donor star to the accelerated mass transfer during the late stages of evolution of Algol-type binaries. We suggest that the observed X-ray activity in Algol-type systems may be a good indicator of their evolutionary status and internal structure of the mass-losing stellar components.     

Molecular orbital models of aqueous aluminum-acetate complexes

Molecular orbital calculations with HF/3-21G^∗∗, HF/6-311+G^∗∗, and MP2/6-311+G^∗∗ basis sets (HF = Hartree-Fock approximation; MP2 = 2nd-order Møller-Plesset perturbation theory) have been performed on molecular clusters in the system acetate-aluminum-water. The results model the structures, energetics, and vibrational spectra of Al³⁺ and Al³⁺-acetate complexes in the aqueous phase. An octahedral to tetrahedral coordination change is predicted in the species Al³⁺ (OH)_m⁻ · n (H₂O) [where m + n = 6) as m increases from two to three. Calculated reaction energetics for aqueous Al³⁺-acetate complexation compare favorably with experimental enthalpies. In addition, the possible existence of more than one configuration for each Al` -acetate species was investigated. Theoretical vibrational spectra of the Al³⁺-acetate complexes provide predictions for the identification of Al³⁺-acetate species in aqueous solutions.