Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.     

Modellversuche zur Hangtektonik

Zusammenfassung Das Verformungsverhalten von Felshängen wird einmal durch die geologische Entwicklungsgeschichte, zum anderen durch die zum Zeitpunkt der Beobachtung herrschenden Randbedingungen (Höhe, Neigung des Hanges, eingeprägte Kräfte) und Gebirgseigenschaften bestimmt. Diese Gebirgseigenschaften sind einerseits von den Gesteinseigenschaften (Verformbarkeit und Festigkeit) und andererseits von der Klüftung abhängig.Mit Hilfe zweidimensionaler großmaßstäblicher Modelle, die in einer ersten Serie aus starren Kluftkörpern (Strukturmodelle) und in einer zweiten Serie aus äquivalentem Modellmaterial aufgebaut waren, wird der Versuch unternommen, die innere Kinematik eines ganzen Hangquerschnittes zu studieren. Während im ersten Fall der Einfluß des Trennflächengefüges allein untersucht werden kann, überlagern sich im zweiten Fall Material- und Gefügeparameter.Anhand der Strukturmodelle wird eine Einteilung in verschiedene typische Verformungsverhalten von Hängen in Abhängigkeit von der Kluftstellung und vom Kluftreibungswinkel vorgenommen.Der besonders interessante Fall eines Kluftkörperverbandes mit bergeinwärtsfallender Bankung — hier überlagern sich Rotations- und Translationsbewegungen — wird in seinem gesamten Verformungsablauf beschrieben und nach charakteristischen Verformungsstadien unterteilt. Dabei wird die Entwicklung der Verformungen vom Hakenwerfen der Böschungsfront bis zu einem tiefgreifenden Talzuschub mit der Ausbildung ausgeprägter Schwächezonen erfaßt.Die an den Versuchen durchgeführten Beobachtungen gestatten eine bessere Bewertung des Trennflächeneinflusses auf das Verformungsverhalten von Felsmassen mit regelmäßigem Gefügemuster (H-Typ) und geben Hinweise zur besseren Abschätzung des Verformungsablaufes im Inneren eines Hanges sowie der zu erwartenden Form des Böschungsbruchkörpers.

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The deformation behaviour of rock slopes is influenced by the geological history, by the boundary conditions (height, inclination of the slope, additional forces) acting at the time of observation and the material properties of the rock mass. The properties depend on the rock parameters (deformability and strength) and on the joint patterns.With two-dimensional large scale models which consisted of rigid blocks in the first series of tests (structural models) and of equivalent model material in a second one, it was tried to study the kinematics of a whole slope section.In the first of those cases joint fabric is the only parameter to be investigated while in the second, series of test material and structural parameters have to be considered simultaneously. The structural models allow a classification into different types of deformation behaviour of the slopes. Criteria of classifications are the inclination of the strata and the friction angle.The especially interesting case of a jointed rock system with strata dipping into the mountain (in this case rotational and translational displacements are superposed) is described in its whole deformation history which is divided into characteristic stages of deformation. The development of displacements is studied from a first Hakenwerfen at the front of the slope to a deep Talzuschub with the formation of zones of weakness (latent sliding surfaces).Conclusions drawn from these tests allow a better assessment of the influence of joint sets on the deformation behaviour of a rock mass, the development of displacements in the interior of a slope and the shape of sliding surfaces.

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Résumé Le processus de déformation des versants rocheux est déterminé d'abord par l'histoire géologique, ensuite par les conditions immédiates du milieu régnant au moment de l'observation (hauteur, inclinaison de la pente, forces emmagasinées) et par les propriétés à l'échelle de l'ensemble rocheux. Ces dernières dépendent d'une part des propriétés du matériau rocheux lui-même (déformabilité et résistance) et d'autre part de la fissuration.A l'aide de maquettes bidimensionelles à grande échelle composées, lors d'une première série, de blocs rigides (modèle structural) et lors d'une seconde série, de blocs faits d'un matériau équivalent, on a assayé d'étudier la cinématique interne d'une coupe transversale faite dans un versant. Tandis que dans le premier cas, c'est seulement l'influence de la disposition des plans de division qui a pu être recherchée, dans le second il y a eu superposition des paramètres propres à cette disposition et au matériau.En partant de ces modèles structuraux, on a pu classer les différents types de comportements à la déformation des versants en fonction de la position de fissures et de leur angle de frottement.Le cas particulièrement intéressant d'un complexe fissuré à stratification inclinant vers l'intérieur du versant (ici se superposent en effet les mouvements de rotation et de translation) est décrit intégralement dans le déroulement de sa déformation et subdivisé en stades caractéristiques de déformation. On a pu ainsi saisir le développement des déformations depuis le «Hakenwerfen» du front du talus jusqu'à la poussée en profondeur vers la vallée, avec formation de zones de faiblesse bien marquées.Les observations faites lors des essais permettent de mieux évaluer l'influence des plans de division sur le processus de déformation des masses rocheuses qui ont une structure régulière (type H). Elles donnent des indications pour apprécier plus justement le développement de la déformation dans un versant, et de la forme de la zone de rupture à laquelle il faut s'attendre.

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Frictional Properties and Microstructure of Calcite-Rich Fault Gouges Sheared at Sub-Seismic Sliding Velocities

We report an experimental and microstructural study of the frictional properties of simulated fault gouges prepared from natural limestone (96 % CaCO₃) and pure calcite. Our experiments consisted of direct shear tests performed, under dry and wet conditions, at an effective normal stress of 50 MPa, at 18–150 °C and sliding velocities of 0.1–10 μm/s. Wet experiments used a pore water pressure of 10 MPa. Wet gouges typically showed a lower steady-state frictional strength (μ = 0.6) than dry gouges (μ = 0.7–0.8), particularly in the case of the pure calcite samples. All runs showed a transition from stable velocity strengthening to (potentially) unstable velocity weakening slip above 80–100 °C. All recovered samples showed patchy, mirror-like surfaces marking boundary shear planes. Optical study of sections cut normal to the shear plane and parallel to the shear direction showed both boundary and inclined shear bands, characterized by extreme grain comminution and a crystallographic preferred orientation. Cross-sections of boundary shears, cut normal to the shear direction using focused ion beam—SEM, from pure calcite gouges sheared at 18 and 150 °C, revealed dense arrays of rounded, ~0.3 μm-sized particles in the shear band core. Transmission electron microscopy showed that these particles consist of 5–20 nm sized calcite nanocrystals. All samples showed evidence for cataclasis and crystal plasticity. Comparing our results with previous models for gouge friction, we suggest that frictional behaviour was controlled by competition between crystal plastic and granular flow processes active in the shear bands, with water facilitating pressure solution, subcritical cracking and intergranular lubrication. Our data have important implications for the depth of the seismogenic zone in tectonically active limestone terrains. Contrary to recent claims, our data also demonstrate that nanocrystalline mirror-like slip surfaces in calcite(-rich) faults are not necessarily indicative of seismic slip rates.     

Hydrologic characteristics of lake‐ and stream‐side riparian wetted margins in the McMurdo Dry Valleys,Antarctica

Water is a limiting factor for life in the McMurdo Dry Valleys (MDV), Antarctica. The active layer (seasonally thawed soil overlying permafrost) accommodates dynamic hydrological and biological processes for 10–16 weeks per year. Wetted margins (visually wetted areas with high moisture content) adjacent to lakes and streams are potential locations of great importance in the MDV because of the regular presence of liquid water, compared with the rest of the landscape where liquid water is rare. At 11 plots (four adjacent to lakes, seven adjacent to streams), soil particle size distribution, soil electrical conductivity, soil water content and isotopic signature, width of the wetted margin, and active layer thaw depth were characterised to determine how these gradients influence physicochemical properties that determine microbial habitat and biogeochemical cycling. Sediments were generally coarse‐grained in wetted margins adjacent to both lakes and streams. Wetted margins ranged from 1·04 to 11·01 m in average length and were found to be longer at lakeside sites than streamside. Average thaw depths ranged from 0·12 to 0·85 m, and were found to be deepest under lake margins. Lake margins also had much higher soil electrical conductivity, steeper topographic gradients, but more gradual soil moisture gradients than stream margins. Patterns of soil water δ¹⁸O and δD distribution indicate capillary action and evaporation from wetted margins; margin pore waters generally demonstrated isotopic enrichment with distance from the shore, indicating evaporation of soil water. Lake margin pore waters were significantly more negative in D_XS (D_XS = δD‐8δ¹⁸O) than streamside pore waters, indicating a longer history of evaporation there. Differences between lake and stream margins can be explained by the more consistent availability of water to lake margins than stream margins. Differences in margin characteristics between lakes and streams have important consequences for the microbial habitat of these margins and their functional role in biogeochemical cycling at these terrestrial–aquatic interfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

Solubility of Pt in sulphide mattes: Implications for the genesis of PGE-rich horizons in layered intrusions

The partitioning of Pt in sulphide melt (matte) has been studied as a function of fS₂ and fO₂ at 1200 and 1300 °C. The results show that the solubility of Pt in mattes increases strongly with increasing fS₂ and decreases weakly with increasing fO₂. The increase in Pt solubility with increasing fS₂ is attributed to Pt dissolving in the melt as a sulphide species and the weak inverse dependence of Pt solubility on fO₂ to the diluting effect of increasing O in the melt at high fO₂. These results, coupled with measurements of Pt solubility in silicate melts taken from the literature, allow the calculation of Pt matte/silicate-melt partition coefficients () for a range of conditions pertinent to the formation of Pt-rich horizons in layered intrusions. The calculated values range between 10⁷ and 10¹¹, depending on fO₂ and fS₂, several orders of magnitude higher than previously published values. Our preferred value for for conditions appropriate to the Merensky Reef is 10⁷ and for the Stillwater Pt-rich horizon 10⁸. The new results are consistent with the magmatic hypothesis for Pt-rich horizons in layered intrusions.     

Preparation and charaterization of self-assembled nanoparticles based on linolenic-acid modified chitosan

1 IntroductionHydrophobically modified water-soluble polymers,also known as hydrophobized polymers, are thosemodified by hydrophobic groups such as alkyl,arolkyl, and deoxycholic acid. In water, they canself-aggregate due to their intro- and/or intermolecularhydrophobic interaction. By this process, unique hy-drogel nanoparticles with hydrophobic core and hy-drophilic shell can be prepared, which is a new ap-proach to preparing the monodispersed hydrogelnanoparticles (Whitesides et al., 1991; …