Structural incorporation of Cm(III) in trioctahedral smectite hectorite: A time-resolved laser fluorescence spectroscopy (TRLFS) study

Structural incorporation of the actinide curium in the octahedral layer of the trioctahedral Mg-rich smectite hectorite was studied using time-resolved laser fluorescence spectroscopy. Organo-hectorite nanoparticles were synthesized at 90 °C in the presence of Cm(III). Within 120 h, hectorite particles were formed. Time-resolved laser fluorescence spectroscopy was used to identify Cm(III) species during various synthesis steps and to characterize the structural incorporation mechanism. The formation of a Cm-containing Mg hydroxide precursor and the reaction with aqueous silica in a pH range of 9-10 to form TOT layers were identified to be key steps for trivalent actinide incorporation in hectorite via coprecipitation.     

Der nacheiszeitliche Bergsturz im Kandertal (Schweiz): Alter und Auswirkungen auf die damalige Umwelt

Zusammenfassung. Beim Bau des neuen AlpTransit Lötschberg Basistunnels wurden unter murgangartig verschwemmten Ablagerungen der alten Bergsturzmasse des Kandertals Stillwasserablagerungen mit zahlreichen organischen Resten und Torflagen gefunden. Die ¹⁴C-datierten Resultate der Pollen, Makrorest-, Holz- und Holzkohleanalysen ermöglichten eine Rekonstruktion der lokalen bis regionalen Umweltgeschichte. Ein Gewässer, vermutlich ein kleiner See, begann beim Tellenfeld in Frutigen um 8800 kal. Jahre v. Chr. zu verlanden. In der näheren Umgebung wuchs von 8800 v. Chr. bis 8000 v. Chr. ein Föhrenwald (Pinus silvestris), der reichlich mit Hasel (Corylus avellana) und anderen wärmeliebenden Gehölzen (Ulmen, Linden, Eichen; Ulmus, Tilia, Quercus) und Birken (Betula) durchsetzt war. Diese für die Nordalpen sehr frühe Bedeutung der Hasel ist durch ¹⁴C-datierte Corylus-Nussfragmente (9310±50 ¹⁴C BP, 8722–8337 v. Chr.) belegt. Nach 8500 v. Chr. drängte die Hasel die Waldföhre allmählich zurück. Auf Grund der paläoökologischen Resultate muss angenommen werden, dass die Wälder um 7600 v. Chr. durch ein katastrophales Ereignis stark gestört wurden. Als Reaktion darauf kam es zu einer starken Zunahme der Waldbrände und es breiteten sich zuerst Farne und Gräser sowie wenig später Waldföhren aus. Das Gewässer wurde um 7100 v. Chr. durch verschwemmtes Bergsturzmaterial zerstört. Der geomorphologische Befund deutet darauf hin, dass diese Ereignisse in engem Zusammenhang mit dem Hauptbergsturz im Kandertal stehen, der aussergewöhnliche Ausmasse hatte (ca. 800 Millionen m³). Die Zerstörung der lokalen ökosysteme als Folge des Bergsturzes um 7600–7100 v. Chr. fiel in ein frühes holozänes Wärme- und Sonneneinstrahlungsmaximum, in dem es, wie vorgängige Untersuchungen in den Alpen und in anderen Gebirgen belegen, zu überdurchschnittlich vielen Hanginstabilitäten kam.

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During the construction of the new AlpTransit railway line wetland sediments containing numerous fossils and peat layers were found below rockfall masses transported by debris flows. Radiocarbon-dated results of pollen, macrofossils, wood, and charcoal along with radiocarbon dating analysis were used to reconstruct the environmental history of the site. The wetland, originally probably a small lake, started to accumulate sediments at about 8800 cal. yr BC at Frutigen Tellenfeld. A pine forest (Pinus silvestris) admixed with hazel (Corylus avellana), other thermophilous arboreal taxa (Ulmus, Tilia, Quercus) and birch (Betula) grew in the surroundings of the lake. This very early importance of hazel is documented by ¹⁴C-dated Corylus nut fragments (9310±50 ¹⁴C yr BP, 8722–8337 yr BC). After 8500 BC hazel expanded on the costs of pine. The palaeo records suggest that the forests were severely disturbed by a catastrophic event at around 7600 BC. In response, forest fires strongly increased and ferns and grasses expanded and then pine stands established. At ca. 7100 BC the lake was abruptly destroyed by rockfall masses transported by a debris flow. The geomorphic situation suggests that these events were closely related with the main Kander valley rockfall, which had an exceptional size (800 millions m³). Local environmental catastrophes as a consequence of the rockfall at 7600–7100 BC occurred during an early Holocene thermal and solar irradiation maximum. As documented by previous investigations, this period was characterised by pronounced slope instabilities in the Alps and elsewhere.

Manuskript eingegangen 9. Februar 2004 Revidierte Fassung angenommen 17. Januar 2005     

Tree Species Composition in European Pristine Forests: Comparison of Stand Data to Model Predictions

The degree of general applicability across Europe currently achieved with several forest succession models is assessed, data needs and steps for further model development are identified and the role physiology based models can play in this process is evaluated. To this end, six forest succession models (DISCFORM, ForClim, FORSKA-M, GUESS, PICUS v1.2, SIERRA) are applied to simulate stand structure and species composition at 5 European pristine forest sites in different climatic regions. The models are initialized with site-specific soil information and driven with climate data from nearby weather stations. Predicted species composition and stand structure are compared to inventory data. Similarity and dissimilarity in the model results under current climatic conditions as well as the predicted responses to six climate change scenarios are discussed. All models produce good results in the prediction of the right tree functional types. In about half the cases, the dominating species are predicted correctly under the current climate. Where deviations occur, they often represent a shift of the species spectrum towards more drought tolerant species. Results for climate change scenarios indicate temperature driven changes in the alpine elevational vegetation belts at humid sites and a high sensitivity of forest composition and biomass of boreal and temperate deciduous forests to changes in precipitation as mediated by summer drought. Restricted generality of the models is found insofar as models originally developed for alpine conditions clearly perform better at alpine sites than at boreal sites, and vice versa. We conclude that both the models and the input data need to be improved before the models can be used for a robust evaluation of forest dynamics under climate change scenarios across Europe. Recommendations for model improvements, further model testing and the use of physiology based succession models are made.     

Effect of siderophores on the light-induced dissolution of colloidal iron(III) (hydr)oxides

Siderophores play an important role in biological iron acquisition in iron-limited aquatic systems. While it is widely accepted that the solubilization of iron-bearing mineral phases is a key function of siderophores, the mechanism of siderophore-promoted mineral dissolution in aquatic systems is largely unknown. In this study, we investigated the effect of siderophores (desferrioxamine B (DFOB) and aerobactin) on light-induced dissolution of goethite and lepidocrocite in the presence or absence of oxalate in aerated and deaerated suspensions at pH 6. For the irradiated two-ligand system (oxalate/siderophore), the experimental results suggest that oxalate acts as the electron donor for the formation of surface Fe(II), and the siderophore acts as an efficient shuttle for the transfer of surface Fe(II) into solution. Furthermore, even in the absence of an electron donor such as oxalate, both DFOB and aerobactin accelerated the light-induced dissolution of lepidocrocite as compared to the thermal dissolution. Experiments with dissolved Fe(III)–DFOB and Fe(III)–aerobactin complexes suggest that this enhancing effect is not due to photolysis of corresponding surface complexes but to efficient transfer of reduced surface Fe(II) into solution, where surface Fe(II) may be formed, e.g., through photolysis of surface Fe(III)–hydroxo groups. Based on this study, we conclude that the interplay of light and siderophores may play a key role in the dissolution of colloidal iron(III) (hydr)oxides in marine systems, particularly in the presence of efficient electron donors.     

Thermodynamic properties of Zn(Al,Cr)2O4 spinels at high temperatures and pressures

Three Al-Cr exchange isotherms between Zn(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 900°, 1100°, and 1300° C, at a total pressure of 25 kbar. Employing data on the equation of state of corundum (Chatterjee et al. 1982), the experimental results were evaluated thermodynamically. It was found that the thermodynamic mixing properties of Zn(Al, Cr)₂O₄ spinels are best described in terms of a symmetric Margules equation. The T- and P- dependence of the Margules Parameter, W _G ^Sp , and of ΔG^* of the exchange reaction, 1/2 ZnAl₂O₄ + 1/2 Cr₂O₃ = 1/2 ZnCr₂O₄+1/2 A1₂O₃, are found to be ΔG ^*=1493?2.869·T+0.0081·P and W _G ^Sp (J/mol)=23456+0.0386·P, with T given in K and P in bar.     

Comparison of production and degradation of organic matter at a littoral site of the prealpine Lake Constance

Biotic structures and processes of the comparatively large and deep Lake Constance are dominated by pelagic water bodies. Therefore, much more attention has thus far been paid to the carbon cycle of pelagic habitats as compared to littoral areas. Nevertheless, there is also an ongoing debate on the importance of littoral areas for the carbon cycle in this lake. Although actually existing data are certainly insufficient for a realistic carbon budget, investigations made during the past decade provide at least a rough basis for a first evaluation. Accordingly, littoral areas appear to contribute overproportionally (related to surface) both to production as well as to degradation of organic carbon in the lake. However, the relative effect seems to be more pronounced for heterotrophic activities, mostly due to intense degradation processes in littoral sediments. Related to volume, littoral water bodies exhibited similar or slightly higher microbial activities as compared to epilimnetic pelagic water bodies, while microbial abundances and activities observed for littoral sediments exceeded the corresponding overlying water layers by one to three orders of magnitude. As was confirmed by in situ measurements microbial oxygen consumption frequently exceeded photosynthetic oxygen production in the investigated littoral sites. Moreover, significant qualitative differences between water and sediment were found for the degradation potentials of xenobiotics as was exemplified for phenol and nitrilo-triacetic acid (NTA). Overall, a buffer function at the landwater interface may be ascribed to littoral areas due to which the large pelagic water bodies of the lake may become additionally protected against loads of undesired organic substances due to high littoral degradation capacities.     

Correlation Between Compositional Parts Based on Symmetric Balances

Correlation coefficients are most popular in statistical practice for measuring pairwise variable associations. Compositional data, carrying only relative information, require a different treatment in correlation analysis. For identifying the association between two compositional parts in terms of their dominance with respect to the other parts in the composition, symmetric balances are constructed, which capture all relative information in the form of aggregated logratios of both compositional parts of interest. The resulting coordinates have the form of logratios of individual parts to a (weighted) “average representative” of the other parts, and thus, they clearly indicate how the respective parts dominate in the composition on average. The balances form orthonormal coordinates, and thus, the standard correlation measures relying on the Euclidean geometry can be used to measure the association. Simulation studies provide deeper insight into the proposed approach, and allow for comparisons with alternative measures. An application from geochemistry (Kola moss) indicates that correlations based on symmetric balances serve as a sensitive tool to reveal underlying geochemical processes.     

Improvement of HVSR technique by wavelet analysis

In this work we investigate the application of the wavelet analysis to improve the well-known horizontal to vertical spectral ratio (HVSR) technique for site effect estimation. Wavelet analysis has been widely used in the last decade for its capacity to localise the signal in both the time and frequency domains. The wavelet packet transform and the evaluation of a cost function for every node permit one to remove from the signal the least important components and lead to significant improvements in the identification of the fundamental frequency. In this paper a new algorithm is presented based on wavelet analysis, that allows, in some cases, to improve the identification of the peak in the QTS ratio. A number of examples of application are also presented.