Redox front geochemistry and weathering: theory with application to the Osamu Utsumi uranium mine, Poços de Caldas, Brazil

Numerical calculations describing weathering of the Poços de Caldas alkaline complex (Minas Gerais, Brazil) by infiltrating groundwater are carried out for time spans up to two million years in the absence of pyrite, and up to 500,000 years with pyrite present. Deposition of uranium resulting from infiltration of oxygenated, uranium bearing groundwater through the hydrothermally altered phonolitic host rock at the Osamu Utsumi uranium mine is also included in the latter calculation. The calculations are based on the quasi-stationary state approximation to mass conservation equations for pure advective transport. This approximation enables the prediction of solute concentrations, mineral abundances and porosity as functions of time and distance over geologic time spans. Mineral reactions are described by kinetic rate laws for both precipitation and dissolution. Homogeneous equilibrium is assumed to be maintained within the aqueous phase. No other constraints are imposed on the calculations other than the initial composition of the unaltered host rock and the composition of the inlet fluid, taken as rainwater modified by percolation through a soil zone. The results are in qualitative agreement with field observations at the Osamu Utsumi uranium mine. They predict a lateritic cover followed by a highly porous saprolitic zone, a zone of oxidized rock with pyrite replaced by iron-hydroxide, a sharp redox front at which uranium is deposited, and the reduced unweathered host rock. Uranium is deposited in a narrow zone located on the reduced side of the redox front in association with pyrite, in agreement with field observations. The calculations predict the formation of a broad dissolution front of primary kaolinite that penetrates deep into the host rock accompanied by the precipitation of secondary illite. Secondary kaolinite occurs in a saprolitic zone near the surface and in the vicinity of the redox front. Gibbsite forms a bi-modal distribution consisting of a maximum near the surface followed by a thin tongue extending downward into the weathered profile in agreement with field observations. The results are found to be insensitive to the kinetic rate constants used to describe mineral reactions.

Die politischen Flickschneider: Der Rock des heiligen Römischen oder Deutschen Reiches war schon vor längerer Zeit mürbe geworden ...

Welsch (Projektbearbeiter): Vergleich der politischen Verfaßtheit Deutschlands mit einem alten, mottenzerfressenen Rock, der aus 38 Flicken besteht und den die politischen Flickschneider nicht zusammenzunähen in der Lage sind. Die Lösung dieser verfahrenen Situation liegt darin, daß der deutsche Michel die Flickschneider davonjagt, die Flicken zusammenwalkt und sich daraus einen neuen, gut sitzenden Rock schneidert

Patterns of landscape form in the upper Rhône basin, Central Swiss Alps, predominantly show lithologic controls despite multiple glaciations and variations in rock uplift rates

The development of topography depends mainly on the interplay between uplift and erosion. These processes are controlled by various factors including climate, glaciers, lithology, seismic activity and short-term variables, such as anthropogenic impact. Many studies in orogens all over the world have shown how these controlling variables may affect the landscape's topography. In particular, it has been hypothesized that lithology exerts a dominant control on erosion rates and landscape morphology. However, clear demonstrations of this influence are rare and difficult to disentangle from the overprint of other signals such as climate or tectonics. In this study we focus on the upper Rhône Basin situated in the Central Swiss Alps in order to explore the relation between topography, possible controlling variables and lithology in particular. The Rhône Basin has been affected by spatially variable uplift, high orographically driven rainfalls and multiple glaciations. Furthermore, lithology and erodibility vary substantially within the basin. Thanks to high-resolution geological, climatic and topographic data, the Rhône Basin is a suitable laboratory to explore these complexities. Elevation, relief, slope and hypsometric data as well as river profile information from digital elevation models are used to characterize the landscape's topography of around 50 tributary basins. Additionally, uplift over different timescales, glacial inheritance, precipitation patterns and erodibility of the underlying bedrock are quantified for each basin. Results show that the chosen topographic and controlling variables vary remarkably between different tributary basins. We investigate the link between observed topographic differences and the possible controlling variables through statistical analyses. Variations of elevation, slope and relief seem to be linked to differences in long-term uplift rate, whereas elevation distributions (hypsometry) and river profile shapes may be related to glacial imprint. This confirms that the landscape of the Rhône Basin has been highly preconditioned by (past) uplift and glaciation. Linear discriminant analyses (LDAs), however, suggest a stronger link between observed topographic variations and differences in erodibility. We therefore conclude that despite evident glacial and tectonic conditioning, a lithologic control is still preserved and measurable in the landscape of the Rhône tributary basins.

Influence of sample matrix on the alkaline extraction of Cr(VI) in soils and industrial materials

An accurate and efficient determination of the highly toxic Cr(VI) in solid materials is important to determine the total Cr(VI) inventory of contaminated sites and the Cr(VI) release potential from such sites into the environment. Most commonly, total Cr(VI) is extracted from solid materials following a hot alkaline extraction procedure (US EPA method 3060A) where a complete release of water-extractable and sparingly soluble Cr(VI) phase is achieved. This work presents an evaluation of matrix effects that may occur during the hot alkaline extraction and in the determination of the total Cr(VI) inventory of variably composed contaminated soils and industrial materials (cement, fly ash) and is compared to water-extractable Cr(VI) results. Method validation including multiple extractions and matrix spiking along with chemical and mineralogical characterization showed satisfying results for total Cr(VI) contents for most of the tested materials. However, unreliable results were obtained by applying method 3060A to anoxic soils due to the degradation of organic material and/or reactions with Fe2+-bearing mineral phases. In addition, in certain samples discrepant spike recoveries have to be also attributed to sample heterogeneity. Separation of possible extracted Cr(III) by applying cation-exchange cartridges prior to solution analysis further shows that under the hot alkaline extraction conditions only Cr(VI) is present in solution in measurable amounts, whereas Cr(III) gets precipitated as amorphous Cr(OH)3(am). It is concluded that prior to routine application of method 3060A to a new material type, spiking tests are recommended for the identification of matrix effects. In addition, the mass of extracted solid material should to be well adjusted to the heterogeneity of the Cr(VI) distribution in the material in question.

Der blutige Rock Josefs [Illustration]

H. Vernet

Der blutige Rock [Illustration]

Velasquez

Der blutige Rock Josefs [Illustration]

Harmensz van Rhin Rembrandt

Der heilige Rock zu Trier und die zwanzig andern heiligen ungenähten Röcke : eine historische Untersuchung

von J. Gildemeister und H. von Sybel