The influence of ionic radii of cations and covalent forces on the unit cell dimensions of spinels

Fe-, Cr- and Al-spinels were synthesized and their unit cell sizes determined by means of X-rays. Differential thermal curves show that the magnetic inversion of Fe₂O₃ at 680° C accelerates the formation of the ferrites when the constituent oxides are heated together.A correlation can be made between ionic radii of cations and unit cell dimensions provided the effect of covalent forces in the lattice is taken into account. The values for ionic radii of cations as given byAhrens (1952) permit a better correlation than those ofGoldschmidt.A shrinkage of 0.01 Å in the unit cell size per 0.01 Å decrease in the ionic radius of the divalent cations was determined when spinels with the same cation arrangement in the same group were compared. A shrinkage of 0.027 Å in the unit cell size per 0.01 Å decrease in the ionic radius of the trivalent cations was determined in spinels having the same divalent cation and cation arrangement when the trivalent cations form the same type of bonds.The half-occupation of the 3d orbits in Mn²⁺ and Fe³⁺ causes abnormally high unit cell dimensions in spinels where these ions are incorporated in octahedral sites. This is attributed to the formation of electrovalent bonds by these ions. Variable forces of contraction in the lattice are revealed when the unit cell dimensions are correlated with the ionic radii of cations. The force of contraction can be satisfactorily explained as being due to covalent forces in the spinel structure. The magnitude of this force or the degree of covalence in the bonds increases in the following order of cations where these are situated in tetrahedral sites:The divalent transition element ions, Fe²⁺, Co²⁺ and Ni²⁺; the B-Sub-group element ions Cd²⁺ and Zn²⁺; Fe³⁺ in tetrahedral co-ordination.     

Die spannungsoptische Meßpatrone in ihrer Anwendung im gebirgsmechanischen Modellversuch

ZusammenfassungDie spannungsoptische Meßpatrone in ihrer Anwendung im gebirgsmechanischen Modellversuch Die in den letzten Jahren für in-situ-Messungen von Gebirgsspannungen entwickelte spannungsoptische Meßpatrone kann in entsprechender Ausführung auch in Modelle für gebirgsmechanische Untersuchungen eingesetzt werden. Die Anwendung im Modellversuch, die Eichung und ein Beispiel werden erläutert.

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SummaryThe Hard-Inclusion Stressmeter and Its Use in Rock Mechanical Model Tests The hard-inclusion stressmeter, developed during recent years for determination of in-situ stress in rock masses, is in principle applicable also to model tests. This application, the calibration and an example are described.

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Vortrag, gehalten beim XIX. Geomechanik-Kolloquium am 16. Oktober 1969 in Salzburg.

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Mit 6 Abbildungen     

Zur Trias des Iran

Zusammenfassung In der Faziesentwicklung der iranischen Trias spiegelt sich der tektonische Zustand und die paläogeographische Position der Arabischen-, der Iran- und der Turan Platte wider. Die Iran Platte bildete während des Paläozoikums mit der Arabischen Platte eine Einheit und wurde durch die Paläotethys von der Turan Platte getrennt. Im Jungpaläozoikum bzw. zu Beginn der Trias löste sie sich aus diesem Verband und kollidierte gegen Ende der Mitteltrias mit der Turan Platte. Die ehemaligen Plattengrenzen werden heute durch die Nordiran Sutur markiert.Unter Berücksichtigung neuer paläotektonischer Ergebnisse werden folgende Fazieszonen unterschieden: Trias des Zagros-Gebietes (Arabische Platte), Trias des Alborz und Zentral-Iran (Iran Platte), Trias des südkaspischen Gebietes, des Kopet Dagh und von Nakhlak (Turan Platte). Die Faziesentwicklungen der Iran- und der Turan-Platte unterschieden sich während der Unter und Mittel-Trias erheblich. Auf der Iran-Platte bestand eine Karbonat-Plattform. Auf dem absinkenden Südrand der Turan-Platte hingegen wurden mächtige (1000–3000 m) klastische, zum Teil marine Sedimente deponiert. Nach der Kollision beider Platten erfolgte eine weitgehende Faziesangleichung in der Obertrias.Die kollisionsbedingten Deformationen (frükimmerische Bewegungen) hatten auf der Turan-Platte orogenen Charakter, auf der Iran-Platte bewirkten sie Hebungen und eine verstärkte Erosion.Da die Iran Platte im Jura durch spreading Vorgänge unter partiellen Rotationen in Teilschollen zerlegt wurde, muß zur paläogeographischen Rekonstruktion eine konstruktive Rückformung dieser Dislokationen durchgeführt werden. Hierbei kommt der Zentral-Ost-Iran Mikroplatte besondere Bedeutung zu.Die Iran Platte und der afghanische Block haben in der oberen Trias als Bestandteil Eurasiens zu gelten. Die Neotethy öffnete sich zwischen der Arabischen und der Iran Platte.

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The facies domains of the Iranian Triassic reflect the tectonic stage and paleogeographic position of the Arabian, Iran and Turan plates. In the Paleozoic Iran and Arabian plate formed a coherent unit and were separated from Turan plate by the Paleotethys. In Late Paleozoic or at the beginning of Triassic the Iran plate drifted apart by the opening of the Neotethys and collided with the Turan plate at the end of the Middle Triassic. The former plate margins are marked at present by the North-Iran suture.Considering new paleotectonic results the following facies types have been distinguished: Triassic of Zagros (Arabian plate), Triassic of Alborz and Central Iran (Iran plate), Triassic of South Caspian area, Kopet Dagh and Nakhlak (Turan plate). The Lower and Middle Triassic facies types of Iran and Turan plate are significantly different. On Iran plate cabonate platform conditions dominated whereas thick (1000–3000 m) clastic partly marine sediments were deposited on the subsiding margin of Turan plate.The collision induced deformations of the Turan plate (Early Kimmerian movements) were of orogenetic type, on the Iran plate however this tectonic event caused uplifting and strong erosion. In Jurassic the Iran plate was fragmented under partial block rotations. Therefore paleogeographic considerations require the reconstruction of the original tectonic situation. In this procedure the Central-East Iran microplate is of special interest. In Late Triassic the Iran plate and the Afghan block were constituents of Eurasia. The Neotethys opened between the Arabian and the Iran plate.

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Résumé Le développement des facies du Trias d'Iran reflète la situation tectonique et la position paléogéographique de la plaque turanienne, la plaque iranienne et la plaque arabe. Pendant le Paléozoïque la plaque iranienne et la plaque arabe formaient un ensemble, qui était séparé de la plaque turanienne par la Paléotéthys. A la fin du Paléozoïque, ou au début du Trias, la plaque iranienne se détachait de cet ensemble et entrait en collision vers la fin du Trias moyen avec la plaque turanienne. Les anciens confins des plaques sont aujourd' hui marqués par la suture nord-iranienne.En raison des nouveaux résultats paléotectoniques, on distingue les zones de faciès suivantes: Le Trias de la région du Zagros (plaque arabe), le Trias de l'Alborz et de l'Iran central (plaque iranienne), le Trias de la région sud-caspienne, Kopet Dagh, Nakhlak (plaque turanienne). Pendant le Trias moyen et inférieur le développement des facies des plaques iranienne et eurasienne différait considérablement. Sur la plaque iranienne existait une plate-forme carbonatique. Sur le bord méridional de la plaque eurasienne, qui était en subsidence lente, des sédiments clastiques épais (1000–3000 m), en partie marins, étaient par contre déposes. Après la collision des deux plaques les différences entre les deux faciès se perdaient durant le Trias supérieur.Les déformations produites par la collision (mouvements kimmériens précoces) avaient un caractère orogénique sur la plaque turanienne, alors qu'elles causaient, sur la plaque iranienne, un soulèvement et une accentuation de l'érosion.La plaque iranienne se décomposait en plusieurs fragments durant le Jurassique sous l'influence du spreading accompagné par des rotations partielles. Pour la reconstruction de la paléographie ces rotations doivent être prises en considération. Dans cette procédure le rôle de la microplaque de l'Iran central et oriental est d'une importance particulière. Pendant le Trias supérieur la plaque iranienne et le bloc de l'Afghanistan faisaint partie de l'Eurasie. La Néotéthys s'ouvrait entre les plaques arabe et iranienne.

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Diatom assemblages and quantitative reconstruction for paleosalinity from a sediment core of Chencuo Lake,southern Tibet

Changing salinity in lakes and especially in closed lakes depends mainly on the balance between precipitation, runoff and evaporation in arid and semi-arid areas, hence influencing lake levels di-rectly[1-4]. Past salinity has been recovered by a vari-ety of environmental indicators from lake sediments such as diatoms, chironomids, ostracoda, isotopes of ostracoda shells, geochemistry, and isotopes of authi-cabonates[3,5—10]. Recently, with extensive data-base study on diatom-salinity transfe…     

Modeling historical climate variability and slope stability

This study presents scenario models for historical variations of climate and slope stability. A model for historical annual patterns of temperature and rainfall was established on the basis of seasonal proxies. A process-based, spatio-temporal model for groundwater variations and slope stability was developed using the GIS environment of the software PCRaster. We applied the slope stability model to study the effects of the different climate scenarios on slope stability for three different hillslopes in the area around Bonn (Germany). The findings indicate three climatic phases with different annual temperature and precipitation patterns over the historic period. The modeling results show that a climatic scenario representing unstable conditions of a transition from the more humid Little Ice Age to dryer recent climate produces the highest slope instabilities. The intensity of this impact, however, varies with the sensitivity of the geomorphic system, i.e. local landforms and lithology, and cannot be generally related to the stability of a specific hillslope. More unstable areas are not necessarily more sensitive to climatic changes: the location of permeable layers (prone to groundwater rise) in relation to sensitive layers (lower strength) and higher gradients (higher stress) influences the sensitivity of a site with respect to climate changes. The presented method is capable of modeling landscape sensitivity to climate change with respect to groundwater-controlled landslides.     

Tracking Holocene environmental changes in an alpine lake sediment core: application of regional diatom calibration, geochemistry, and pollen

Diatom abundances in the surface sediment samples of 41 mountain lakes in the central Austrian Alps (Niedere Tauern) were related to environmental variables using multi-variate techniques. Canonical correspondence analysis (CCA) revealed that the pH, date of autumn mixing (A _mix), mean August water temperature (T _Aug), dissolved organic carbon (DOC), and relative water depth (Z _rel) made significant contributions to explain the diatom assemblage variation in the lakes of the training set. A weighted averaging partial least square regression and calibration model was used to establish Di-pH (R ² _boot= 0.72, RMSEP_boot= 0.131), and a thermistor measurements-based PLS model for A _mix (R ² _boot= 0.71, RMSEP_boot= 0.006 log₁₀ Julian days). The latter showed a better prediction than T _Aug, and was used in terms of climate change. These transfer functions, together with analyses of loss on ignition (LOI), the total carbon/nitrogen (C/N)-ratios, and selected pollen, were applied to an early to mid-Holocene (11.5–4 cal. ky BP) sediment core section from an Austrian Alpine treeline lake on crystalline bedrock. Additionally, passive sample scores in the CCA of the diatom training set were used to show trends in the variables DOC and Z _rel. During the early Holocene, diatoms indicative of increased pH, extended warm summers, and low water levels dominated. Between 10.2 and 7.6 cal. ky BP it was followed by diatom assemblages that indicated an increase in lake water depth and an earlier A _mix. The multi-proxy data suggest that the A _mix decline is the result of a series of snow-rich summer cool and wet climate fluctuations, which were divided by climate warming at ∼9 cal. ky BP. Increased A _mix, LOI and DOC, and the correspondent decline in the C/N-ratios, show subsequent climate warming between 7.3 and 6 cal. ky BP. The long-term trend in Di-pH indicates the impact of catchment-related processes during the early-Holocene, that were superimposed by climate.     

A rocking multianvil: elimination of chemical segregation in fluid-saturated high-pressure experiments

Fluid saturated high-pressure experiments often result in strongly zoned experimental charges, this hinders experimentation in chemically homogeneous systems which in turn has serious consequences on equilibration, reaction progress, and (apparent) phase stabilities. In order to overcome these problems, a 600-ton press accommodating either a multianvil or end-loaded piston cylinder module has been mounted in such a way that it can be turned by 180°, thus inverting its position in the gravity field. During turning, hydraulic pressure, heating power, and cooling water remain connected allowing fully controlled pressures and temperatures during experiments.A series of experiments at 13 GPa, 950°C, on a serpentine bulk composition in the MgO-SiO₂-H₂O system demonstrates that continuous turning at a rate of 2 turns/min results in a nearly homogeneous charge composed of phase E + enstatite. The same experiment at static conditions resulted in four mineral zones: quench phase E, enstatite, enstatite + phase E, and phase E + phase A. Phase A disappears in experiments at a turning rate ≥1 turn/min. A static 15-min experiment shows that zonation already forms within this short time span. Placing two short capsules within a single static experiment reveals that the fluid migrates to the hot spot in each capsule and is not gravitationally driven toward the top. The zonation pattern follows isotherms within the capsule, and the degree of zonation increases with temperature gradient (measured as 10 °C within a capsule) and run time.Our preferred interpretation is that Soret diffusion causes a density-stratified fluid within the capsule that does not convect in a static experiment and results in temperature dependant chemical zonation. The aggravation of zonation and appearance of additional phases with run time can be explained with a dissolution-reprecipitation process where the cold spot of the capsule is relatively MgO enriched and the hot spot relatively SiO₂ and H₂O enriched (at 13 GPa and 950°C). Rocking and tilting of a stratified fluid induces Rayleigh-Taylor instabilities, causing chemical rehomogenization. If turning is faster than the time required to build significant chemical potential gradients in the fluid, chemical zonation in the distribution of the solids is suppressed.     

Mid-latitude Southern Indian Ocean response to Northern Hemisphere Heinrich events

The lack of temporal resolution and accurate chronology of Southern Ocean marine cores has hampered comparison of glacial millennial-scale oscillations between the Southern Ocean, Antarctic ice and other records from both hemispheres. In this study, glacial climate variability is investigated over the last 50 ka using a multi-proxy approach. A precise chrono-stratigraphy was developed on the high-sedimentation rate core MD94-103 (Indian Southern Ocean, 45°35′S 86°31′E, 3560 m water depth) by geomagnetic synchronization between the later core and NAPIS75, and ¹⁴C dates. High-resolution time-series of δ¹⁸O in planktonic foraminifera Globigerina bulloides and Neogloboquadrina pachyderma, and sea surface temperatures (SSTs) estimated from the alkenone U^K′₃₇ index and foraminifera assemblages have been generated. Temporal evolution of the two temperature proxy records is notably different during the last glacial period. While foraminifera data indicate a consistent cooling towards the last glacial maximum, anomalous warm glacial alkenone temperatures suggest a strong advection of warm “detrital” alkenones by surface waters of the Agulhas current. Superimposed to this general trend, during Heinrich events, foraminiferal SSTs point to warmer surface waters, while concurrent alkenone SSTs exhibit apparent coolings probably caused by enhanced local alkenone production. By analogy to modern observations, possible influence of ENSO-like conditions on the subantarctic Southern Ocean SSTs is discussed.     

Oxygen isotope fractionation during synthesis of CaMg-carbonate and implications for sedimentary dolomite formation

Hydrous CaMg-carbonate was synthesized at temperatures of 40°, 60° and 80°C in the laboratory. This material has very similar mineralogical characteristics to natural disordered dolomite from the Coorong region in South Australia. Besides the dolomite variable amounts of amorphous carbonate are present in all samples. The oxygen isotope compositions of synthesized bulk carbonate samples (e.g., amorphous carbonate plus dolomite) plot significantly lower than the Northrop and Clayton (1966) dolomite-water equilibrium. Fractionated degassing of the samples, however, revealed relatively low oxygen isotope values for fast-reacting (using 100% H₃PO₄) amorphous carbonate. In contrast, slow-reacting dolomite has more positive oxygen isotope values, and calculated carbonate-water oxygen isotope fractionation values are close to strongest known dolomite-water oxygen isotope fractionation published earlier on. Variations of reaction/stabilization temperatures during synthesis gave evidence for dolomite formation from hypersaline solutions by a dissolution/reprecipitation process. It is likely that amorphous carbonate has been a problem in defining the dolomite-water fractionation in the past. Moreover, dolomite-associated amorphous carbonate contents probably led to incorrect speculations about lower oxygen isotope fractionation in a so-called protodolomite-water system.