Lippmann Diagrams: Theory and Application to Carbonate Systems

Since 1980 when F. Lippmann's seminal paper appeared, ourunderstanding of solubility equilibria involving ionic solidsolutions has been advanced by theoretical considerations as wellas careful experimental studies designed to determine excess Gibbsfunctions. A unified theory of solid-solution aqueous-solutionequilibria as well as the thermodynamic background of thephenomenon of ``stoichiometric saturation' are reviewed.It is shown that Lippmann diagrams effectively summarize thethermodynamic basis of solid-solute aqueous-solution equilibria ofsparingly soluble metal carbonate systems. Clearly, the predictivepower of these diagrams may be limited due to kineticrestrictions. Only when dissolution and precipitation areessentially reversible, favourable conditions to synthesizehomogeneous solid phases can be derived from studies of equilibria.     

Relevance of Deterministic Structures for Modeling of Transport: The Lauswiesen Case Study

Knowledge of site‐specific contaminant transport processes is an essential requirement for performing various tasks concerning the protection and management of groundwater resources. However, prediction of their behavior is often difficult, especially in heterogeneous aquifers because of the lack of information about flow‐ and transport‐governing subsurface structures and parameters. Hence, stochastic approaches have been developed and frequently used. However, extensive modeling studies on sedimentary structures have shown that consideration of hydrogeological subunits and their distribution can be essential for transport modeling. A case study from the intensely investigated Lauswiesen site is used to demonstrate that more accurate predictions are possible with improved knowledge of deterministic structures. Results of this case study using direct‐push injection logging (DPIL) provide a more reliable characterization of hydraulic conductivity than sieve and flow meter data.     

Diffusive mass exchange of non‐reactive substances in dual‐porosity porous systems – column experiments under saturated conditions

Diffusive mass exchange into immobile water regions within heterogeneous porous aquifers influences the fate of solutes. The percentage of immobile water is often unidentified in natural aquifers though. Hence, the mathematical prediction of solute transport in such heterogeneous aquifers remains challenging. The objective of this study was to find a simple analytical model approach that allows quantifying properties of mobile and immobile water regions and the portion of immobile water in a porous system. Therefore, the Single Fissure Dispersion Model (SFDM), which takes into account diffusive mass exchange between mobile and immobile water zones, was applied to model transport in well‐defined saturated dual‐porosity column experiments. Direct and indirect model validation was performed by running experiments at different flow velocities and using conservative tracer with different molecular diffusion coefficients. In another column setup, immobile water regions were randomly distributed to test the model applicability and to determine the portion of immobile water. In all setups, the tracer concentration curves showed differences in normalized maximum peak concentration, tailing and mass recovery according to their diffusion coefficients. These findings were more pronounced at lower flow rates (larger flow times) indicating the dependency of diffusive mass exchange into immobile water regions on tracers' molecular diffusion coefficients. The SFDM simulated all data with high model efficiency. Successful model validation supported the physical meaning of fitted model parameters. This study showed that the SFDM, developed for fissured aquifers, is applicable in porous media and can be used to determine porosity and volume of regions with immobile water. Copyright © 2015 John Wiley & Sons, Ltd.     

Energy partitioning over a semi‐arid shrubland in northern China

During the last decade, the widely distributed shrublands in northern China have shown significant signs of recovery from desertification, the result of widespread conservation practices. However, to support the current efforts in conservation, more knowledge is needed on surface energy partitioning and its biophysical controls. Using eddy‐covariance measurements made over a semi‐arid shrubland in northwest China in 2012, we examined how surface energy‐balance components vary on diurnal and seasonal scales, and how biophysical factors control bulk surface parameters and energy exchange. Sensible heat flux (H) exceeded latent heat flux (λE) during most of the year, resulting in an annual Bowen ratio (β, i.e. H/λE) of 2.0. λE exceeded H only in mid‐summer when frequent rainfall co‐occurred with the seasonal peak in leaf area index (LAI). Evapotranspiration reached a daily maximum of 3.3 mm day^?1, and summed to 283 mm yr^?1. The evaporative fraction (EF, i.e. λE/R_n), Priestley–Taylor coefficient (α), surface conductance (g_s) and decoupling coefficient (Ω) were all positively correlated with soil water content (SWC) and LAI. The direct enhancement of λE by high vapour pressure deficit (VPD) was buffered by a concurrent suppression of g_s. The g_s played a direct role in controlling EF and α by mediating the effects of LAI, SWC and VPD. Our results highlight the importance of adaptive plant responses to water scarcity in regulating ecosystem energy partitioning, and suggest an important role for revegetation in the reversal of desertification in semi‐arid areas. Copyright © 2015 John Wiley & Sons, Ltd.     

Regional ash fall hazard II: Asia-Pacific modelling results and implications

In a companion paper (this volume), the authors propose a methodology for assessing ash fall hazard on a regional scale. In this study, the methodology is applied to the Asia-Pacific region, determining the hazard from 190 volcanoes to over one million square kilometre of urban area. Ash fall hazard is quantified for each square kilometre grid cell of urban area in terms of the annual exceedance probability (AEP), and its inverse, the average recurrence interval (ARI), for ash falls exceeding 1, 10 and 100?mm. A surrogate risk variable, the Population-Weighted Hazard Score: the product of AEP and population density, approximates the relative risk for each grid cell. Within the Asia-Pacific region, urban areas in Indonesia are found to have the highest levels of hazard and risk, while Australia has the lowest. A clear demarcation emerges between the hazard in countries close to and farther from major subduction plate boundaries, with the latter having ARIs at least 2 orders of magnitude longer for the same thickness thresholds. Countries with no volcanoes, such as North Korea and Malaysia, also face ash falls from volcanoes in neighbouring countries. Ash falls exceeding 1?mm are expected to affect more than one million people living in urban areas within the study region; in Indonesia, Japan and the Philippines, this situation could occur with ARIs less than 40?years.     

Untersuchungen über die Trübungsverhältnisse,die Durchsichtigkeit und die Wasserfarbe in schweizerischen Gewässern

Zusammenfassung Im ersten, der Festlegung der theoretischen Grundlagen der Trübung gewidmeten Kapitel wird die Sinkgeschwindigkeit kleiner Teilchen auf Grund der Gesetze der ?Schwebetheorie? vonWesenberg-Lund, W. Ostwald sowie der Stokesschen Formel diskutiert. Ein weiteres Kapitel orientiert anhand bisheriger Kenntnisse über die Erscheinungen der Lichtdurchl?ssigkeit (bzw.-absorption) und des Lichtklimas in verschiedenen Tiefen unserer Seen. Die Trübung der in einer Reihe von Flu?systemen und Seen erhobenen W?sser wurde mittels der absoluten Messung im Pulfrich-Stufenphotometer festgestellt. Sodann wurden die analysierten Proben nach steigenden Trübungswerten geordnet und unterteilt in ?Klarseen?, ?mitteltrübe? und ?trübe? Seen. Schliesslich wurde zusammen mitH. Züllig der Grad der Trübung, der Transparenz und die Seefarbe zueinander in Beziehung gebracht, wobei unterschieden wird zwischen Seen, die a) durch vorwiegend anorganische Stoffe, b) durch vorwiegendOscillatoria-armes Plankton, c) durch vorwiegendOscillatoria rubescens getrübt sind. Die in mehreren Tabellen und Abbildungen wiedergegebenen Werte der Wassertrübung spiegeln die unterschiedlichen Verh?ltnisse wider, die sich im Laufe einer ausgedehnteren Flu?strecke oder in einem See ergeben aus der Mischung des verschieden stark mit Schwebestoffen belasteten Wassers von Haupt- und Nebenfluss, sodann aus der fortschreitenden oder von Strecke zu Strecke wechselnden Sedimentation, und natürlich auch von der lokalen oder regionalen Wetterlage (Niederschl?ge und Schneeschmelze). In ausgedehnten und zum Teil über Monate hinweg durchgeführten Sedimentationsversuchen im Laboratorium wurde schliesslich der Kl?rvorgang von W?ssern verschiedener Herkunft in Funktion der Zeit untersucht. Dabei ergaben sich unterschiedliche Kurven, die ein Bild zu vermitteln verm?gen über den mittleren Durchmesser der die Trübung verursachenden sedimentierbaren, anorganischen Partikeln.     

MELIMEX,an experimental heavy metal pollution study: Effects of increased heavy metal load on uptake of glucose by natural planctonic communities

Glucose uptake in lake water samples has been determined with short-time¹⁴C-experiments at different additions of the single heavy metals Cu⁺⁺, Zn⁺⁺, Cd⁺⁺, Pb⁺⁺, Hg⁺⁺ and at different additions of a combination of all metals. The degree of a metal induced inhibition of glucose uptake varied from lake to lake and from season to season, whereby the addition of legally tolerated concentrations of 10 μg Cu/l and 200 μg Zn/l inhibited glucose uptake in most samples significantly, as well as the simultaneous addition of all metals. The legally tolerated limit of 1 μg Hg/l inhibited glucose uptake in Lake Lucerne samples almost completely, showed however no effect in samples of Lake Baldegg. The equimolar toxicity sequence of heavy metals for heterotrophic microorganisms has been determined as: Hg>Cu>Cd>(Zn. Pb). Glucose uptake of plankton sampled from metal polluted limno-corrals was less inhibited than that of the control plankton, when heavy metals were added to the samples singly or in combination. It is assumed that this effect is due to the natural selection of more resistant plankton species.     

Natural shock behavior of almandite in metamorphic rocks from the ries crater,Germany

An extensive study of a big number of gneiss specimens with various shock features from the suevite allowed unravelling of the shock behavior of almandite garnets.Almandites in shocked metamorphic rocks show with increasing dynamic pressures strong irregular fracturing. differently oriented sets of planar fractures or elements, brown turbidity and nucleation of minute crystals of an unknown phase in solid garnets. At higher peak pressures garnet was found to break down to (1) orthopyroxene + spinel + glass, and to (2) spinel + glass due to fast shock-melting.Extensive quantitative electron microprobe studies of almandite garnets and their breakdown products were carried out. The breakdown products within the original grain boundaries of the garnets consist of an alumina-rich orthopyroxene (with up to 10 wt. % Al₂O₃), hercynite to pleonaste spinels and a silica and calcium-rich glass matrix. The chemical zonation of magnesium and manganese of the former garnets is inherited in the composition of the newly formed orthopyroxenes.Petrographic evidence and chemical composition suggest a fast breakdown of the almandite garnets after passing of shock waves at rapidly falling pressures and very high post-shock temperatures within the ejected gneissic rock material.