The carbohydrates in relation to mineralogic and granulometric composition of surface sediments in the karst estuary (River Krka estuary,Yugoslavia)

The investigation of mineral, granulometric and chemical composition of sediments of the River Krka estuary (Yugoslavia) were performed in order to elucidate the origin of the sediments and the pattern of sedimentation. Estuarine surface sediments were found to be fine-grained with a bimodal distribution. Environmental conditions in estuarine sediments favour conservation of the organic matter (anoxic conditions). The carbohydrates in the sediments were investigated to determine whether they are of terrigenous or authigenous origin. Glucose, galactose, mannose, xylose, rhamnose, glucosamine and glucuronic acid were detected in the sediments. Their mutual relationship indicates a preferentially terrigenous source of sedimented organic material in estuarine sediments.     

Semi-analytical solutions of a contaminant transport equation with nonlinear sorption in 1D

A new method to determine semi-analytical solutions of one-dimensional contaminant transport problem with nonlinear sorption is described. This method is based on operator splitting approach where the convective transport is solved exactly and the diffusive transport by finite volume method. The exact solutions for all sorption isotherms of Freundlich and Langmuir type are presented for the case of piecewise constant initial profile and zero diffusion. Very precise numerical results for transport with small diffusion can be obtained even for larger time steps (e.g., when the Courant-Friedrichs-Lewy (CFL) condition failed).     

Mineralogical data on a sulphosalt from the Rhodope mountains,Bulgaria

Zusammenfassung Bei dem Versuch, die Kristallstruktur von Bonchevit zu bestimmen, stellte sich heraus, daß dieses Mineral—bis dahin PbBi₄S₇—aus zwei Phasen besteht. Der Hauptanteil wurde eindeutig als Galenobismutit identifiziert. Der Rest wies nach den Gitterkonstanten (a₀=13,58±0,02 Å, b₀=20,51±0,07 Å, c₀=4,09±0,07 Å) auf ein bisher unbekanntes Mineral hin. Die Raumgruppe ist Bbmm. Ein indiziertes Pulverdiagramm und die dazugehörigen d-Werte werden angegeben.Die Emissionsspektralanalyse zeigt Pb und Bi als Hauptkomponenten, Cu und Ag als Nebenkomponenten und Spuren von Zn und Sn. Die Strukturanalyse führte zu der Formel Me₅S₆, wobei die Me-Atome etwa gleich schwer sind, so daß als chemischo Formel nur Pb₃Bi₂S₆ mit Z=4 in Frage kommt.Strukturell gehört das Mineral in die Gruppe Andorit-Ramdohrit-Fizelyit. Die Verwandtschaft bzw. Identität des Minerals mit anderen Mineralen und synthetischen Verbindungen wird diskutiert.

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Mineralogical data on a sulphosalt from the Rhodope mountains, Bulgaria

Summary During an attempt to determine the crystal structure of bonchevite, this mineral was found to consist of two phases. Previously it was thought to have the composition PbBi₄S₇. The main constituent could unambiguously be identified as galenobismutite. For the rest the lattice constants (a₀=13.58±0,02 Å, b₀=20.51±0,07 Å, c₀=4.09±0.07 Å), indicated a new mineral. Space group is Bbmm. An indexed powder diagram (with d-values) is given.The emission spectrographic analysis shows Pb and Bi to be main components, Cu and Ag to be minor components, and traces only of Zn and Sn. The structure analysis has led to the formula Me₅S₆, with Me-atoms of approximately the same atomic number; therefore, the chemical formula has to be Pb₃Bi₂S₆, with Z=4.In a structural classification the mineral belongs to the andoriteramdohrite-fizelyite-group. The relationships to or the identity with other minerals and synthetic compounds are discussed.

     

Biomarker distributions as indicators for the depositional environment of lacustrine sediments in the Valjevo-Mionica basin (Serbia)

In this study, the molecular composition and biomarker distribution of lacustrine sediments from Val-1 drillhole in the central zone of the western part of the Valjevo-Mionica basin were investigated at depth interval of 0–400 m. Former investigations have shown that the core material can be separated into six depth intervals based on bulk geochemical, mineralogical and sedimentological characteristics. Concerning the quality of organic matter, presence of specific minerals, and high salinity and anoxicity, or alkalinity, three zones are of highest interest, defined at depth intervals of 15–75 m (A), 75–200 m (B) and 360–400 m (F). The first aim of the study was to identify which biomarkers characterize these specific intervals. The second aim, addressing the transitions zones of these intervals, was to extend the changes in the characteristics of the organic substance, to reflect the changes of conditions in the depositional environment as well as to define biomarker parameters which are the most sensitive sedimentological indicators.The sediments from the hypersaline anoxic and alkaline environment show high contribution of algal precursor biomass, what is in accordance with the good quality of organic substances in the sediments from these zones. High squalane content and low content of regular isoprenoid C₂₅ are typical for hypersaline anoxic environment, whereas sediments from alkaline environment have high regular isoprenoid C₂₅ content.Transition to specific sedimentation zones is characterized by change in total organic matter content, and of both free and pyrolysis-derived, and change in hydrogen index value. In the biomarker distributions, more significant changes were detected in distributions of n-alkanes and isoprenoids, compared to polycyclic alkanes. The most intensive changes in alkane distribution are reflected in changes in n-C₁₇ content compared to n-C₂₇, and phytane compared to n-C₁₈. In addition, significant sensitivity was seen in ratios between squalane and n-alkane C₂₆ (hypersaline depositional environment), or isoprenoid C₂₅ and n-alkane C₂₂ for high alkalinity environment.This study showed that Sq/n-C₂₆ ratio can be used to assess the quality of organic substance in immature lacustrine sediments.     

Ab initio calculated electron densities for tetrahedral sheet [H2Si2O5]∞ in phyllosilicates

Periodic ab initio Hartree-Fock LCAO calculations have been carried out on the two dimensional sheet of SiO₄ tetrahedra, representing one of the basic constituting units of layer silicates, using Huzinaga's DZP basis sets. The influence of the basis set on the chemical bonding picture is characterized by Mulliken atomic charges and by electron density maps. Silicon atomic charges +1.6 ¦e¦ are more realistic than those +2.4 ¦e¦ reported for smaller basis sets. The silicon d orbital population is found to be 0.6 in close agreement with molecular data. Electron density maps indicate the absence of charge density in the center of the ditrigonal cavity. The charge buildup of nonbonding basal oxygen orbitals is directed mainly downwards perpendicular to the sheet plane.     

Cation exchange capacity of loess and overlying soil in the non-carbonate loess sections, North-Western Croatia

The adsorption properties in terms of cation exchange capacity and their relation to the soil and sediment constituents (clay minerals, Fe-, Mn-, and Al-oxyhydroxides, organic matter) were investigated in loess, soil-loess transition zone, and soil at four loess-soil sections in North-Western Croatia. Cation exchange capacity of the bulk samples, the samples after oxalate extraction of Fe, Mn and Al, and after removal of organic matter, as well as of the separated clay fraction, was determined using copper ethylenediamine. Cation exchange capacity (pH～7) of the bulk samples ranges from 5 to 12 cmol _c /kg in soil, from 7 to 15 cmol _c /kg in the soil-loess transition zone, and from 12 to 20 cmol _c /kg in loess. Generally, CEC values increase with depth. Oxalate extraction of Fe, Mn, and Al, and removal of organic matter cause a CEC decrease of 3–38% and 8–55%, respectively, proving a considerable influence of these constituents to the bulk CEC values. In the separated clay fraction (<2 μm) CEC values are up to several times higher relative to those in the bulk samples. The measured CEC values of the bulk samples generally correspond to the clay mineral content identified. Also, a slight increase in muscovite/illite content with depth and the vermiculite occurrence in the loess horizon are concomitant with the CEC increase in deeper horizons, irrespective of the sample pretreatment.     

Application of the photoacoustic method for characterization of natural galena (PbS)

Electron transport properties of single crystal and polycrystalline natural mineral galena (PbS) samples from the Trep?a mine, Yugoslavia, were determined using the photoacoustic frequency transmission technique. Their thermal diffusivity (D _T≈0.16 × 10^?5 m² s^?1), the coefficient of diffusion (D between 0.15×10^?2 0.16×10^?2 m² s^?1) and lifetime of the excess carrier (τ≈35 μs and the front and rear recombination velocity (s _g≈65.5 m s^?1 and s _b≈66.4 m s^?1, respectively), were calculated by comparing the experimental results and the theoretical photoacoustic amplitude and phase signals. The lattice parameter obtained by X-ray work was a?=5.936?Å. The free carrier concentration of these single-crystal samples was measured using the Hall method (N?=?3×10¹⁸ cm^?3). Measurements of the optical reflectivity of the same samples, as a function of wavelength, in the infrared and far infrared ranges, were performed. In the far infrared range a free electron plasma frequency was observed and numerically analyzed, using the least-squares fitting procedure. The values of optical parameters were calculated and the value of the free carrier concentration obtained by the Hall method was confirmed.