Mechanisms of galena dissolution in oxygen-saturated solutions: Evaluation of pH effect on apparent activation energies and mineral-water interface

This work describes a laboratory investigation of processes ruling the dissolution of galena (PbS) under conditions that mimic oxidising Earth surface environments. Freshly cleaved (001) galena surface was partially dissolved in solutions at different pH (HCl, pH between 1.2 and 5.8) and temperature (298 K) levels for several weeks in a flow-through reactor. Analysis of the galena surface after exposure to oxygen-saturated solutions was performed by XPS. The estimated thickness of surface layer formed after interaction for four weeks with solution at pH 5.8 was ∼0.5 nm. After the same time of interaction with solution at pH 1, the surface layer was at least 9 nm thick. Stationary dissolution rates were measured at different pH (between 1 and 5.8) and temperatures (298, 323, 348 K). Reaction order with respect to hydrogen ion averages 0.6 and slightly decreases with temperature. Dissolution rates, plotted vs. the reciprocal values of temperature, follow Arrhenius behaviour. Activation energies show a sharply discontinuous variation with pH. They are 13.5 ± 2 kJmol⁻¹ at pH = 1.2 and 2.87, whereas at pH of 4.08, 4.7, and 5.8, they show, respectively, values of 48.8 ± 3.5, 45 ± 4, and 51 ± 4 kJmol⁻¹. The apparent activation energy was also investigated by starting the experiment from pH 5.8 and then decreasing to pH 1.2. In this case, the apparent activation energies were 44 ± 4 kJmol⁻¹ and 21 ± 4 kJmol⁻¹, respectively.Apparent activation energies indicate a diffusion-controlled kinetic regime for pH <3, and a mixture of surface and diffusion control for pH between ∼4 and 5.8. A strong effect of solution pH on the mineral-water interface is revealed also by the observed pH dependence of surface-layer thickness. On the basis of the high-resolution XPS signals, the dependence of activation energies on solution pH should reflect a change of structure, and also chemical composition, of the mineral-water interface.     

Geochemical and geochronological data on Triassic volcanism of the Southern Alps of Lombardy (Italy): Genetic implications

Summary A widespread volcanism mainly consisting of pyroclastic products and lava flows is found in the Southern Alps of Lombardy. The volcanics are interbedded with Anisian-Ladinian carbonatic sequences and continental terrigenous or transitional deposits of Ladinian-Carnian age. The petrographic and geochemical data for this volcanism indicate a calc-alkaline affinity with characters similar to those of convergent continental margins. In this sector of the Alps the geological evidences show that in the middle Triassic general extensional movements were the dominant deformation event, and do not support the existence of a subduction zone during this period. The apparent contrast between the tectonic environment and the type of magmas erupted in the Anisian-Carnian is tentatively explained by partial melting during the early stage of rifting of an upper mantle deeply modified during the previous Hercynian orogenesis and contaminated by crustal material. This hypothesis is in agreement with the preliminary Sr isotopic ratios (0.705 and 0.709). K/Ar and Rb/Sr ages on biotites date the beginning of the volcanism at around 225 m.y.

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Zusammenfassung In den Südalpen der Lombardei befindet sich ein weitverbreiteter Vulkanismus, der hauptsächlich aus pyroklastischen Produkten und Lavaströmen besteht. Vulkanische Produkte sind mit anisisch-ladinischen beckenartigen Karbonat-Schichtfolgen oder mit ladinisch-karnischen kontinental-terrestrischen oder Übergangsablagerungen eingebettet. Die petrographischen und geochemischen Daten für diesen Vulkanismus weisen auf eine den konvergenten Kontinentalschelfen ähnliche kalkalkaline Affinität hin. In diesem Sektor der Alpen zeigen die geologischen Beobachtungen, daß die dominanten Verformungsereignisse der mittleren Trias allgemeine Dehnungsbewegungen waren und weisen nicht auf die Existenz einer Subduktionszone zu dieser Zeit hin. Der scheinbare Widerspruch zwischen dem tektonischen Milieu und dem im Anis bis Karn ausgeworfenen Magmatyp wird versuchsweise mit einer Teilaufschmelzung eines während der vorhergehenden herzynischen Orogenese tief veränderten und mit Krustenmaterial verunreinigten oberen Mantels während der Frühphase einer Grabenbildung erklärt. Diese Hypothese ist im Einklang mit den präliminaren Sr-Isotopenverhältnissen (0.705 und 0.709). K/Ar und Rb/Sr Altersmessungen an Biotiten datieren den Anfang der vulkanischen Tätigkeit um 225 Ma.

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Résumé Un volcanisme très répandu constitué surtout par des produits pyroclastiques et par des coulées de lave se trouve dans les Alpes Méridionales en Lombardie. Ces produits volcaniques sont intercalés dans la série carbonatique du bassin d'âge Anisien-Ladinien et dans les dépôts terrigènes continentaux ou transitionnels d'âge Ladinien-Carnien. Les données pétrographiques et géochimiques de ces produits volcaniques montrent une affinité calcoalcaline avec des caractères semblables à ceux des marges continentales convergentes. Dans le Trias moyen de cette partie des Alpes, les données géologiques indiquent que le motif dominant de la déformation est un mouvement d'extension très répandu, tandis qu'il n'y a aucune évidence de l'existence d'une zone de subduction durant cette période. Le contraste entre le style tectonique et le type de magma mis en place dans l'Anisien-Carnien, peut être expliqué par une fusion partielle du manteau supérieur pendant un stade précoce d'effondrement modifié intensément pendant la précédente orogenèse hercynienne et contaminé par des matériaux d'origine crustale. Cette hypothèse est en accord avec des données préliminaires des rapports isotopiques du Sr (0.705 et 0.709). Des âges K/Ar et Rb/Sr sur des biotites donnent 225 m.a. environ pour le début de l'activité volcanique.

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Improving basin scale shallow landslide modelling using reliable soil thickness maps

Soil thickness is a well-known factor controlling shallow landsliding. Notwithstanding, its spatial organisation over large areas is poorly understood, and in basin scale slope analyses it is often established using simple methods. In this paper, we apply five different soil thickness models in two test sites, and we use the obtained soil thickness maps to feed a slope stability model. Validation quantifies how errors in soil thickness influence the resulting factor of safety and points out which method grants the best results. In particular, in our cases, slope-derived soil thickness patterns produced the worst slope stability assessment, while the use of reliable soil thickness maps obtained by means of a more complex geomorphologically indexed model improved shallow landslides modelling.     

Effect of Overstrength on the Seismic Behaviour of Multi-Storey Regularly Asymmetric Buildings

In past years, seismic response of asymmetric structures has been frequently analysed by means of single-storey models, because of their simplicity and low computational cost. However, it is widely believed that use of more realistic multi-storey models is needed in order to investigate effects of some system characteristics (such as overstrength, higher modes of vibration, etc.) that make behaviour of multi-storey schemes different from that of single-storey systems. This paper examines effects of the overstrength in element cross-sections on the seismic behaviour of multi-storey asymmetric buildings. It is shown that in actual buildings this characteristic, which is sometimes very variable both in plan and along the height of the building, may lead to distributions of ductility demands different from those expected according to the results from single-storey models. Consequently, torsional provisions, which aim at reducing ductility demands of single-storey asymmetric systems to those of the corresponding torsionally balanced systems, should be re-checked in light of the behaviour of realistic multi-storey buildings.     

Cartography of the <Emphasis Type="Italic">b</Emphasis>-plane of a close encounter I: semimajor axes of post-encounter orbits

Close planetary encounters play an important role in the evolution of the orbits of small Solar system bodies and are usually studied with the help of numerical integrations. Here we study close encounters in the framework of an analytic theory, focusing on the so-called b-plane, which is the plane centred on the planet and perpendicular to the planetocentric velocity at infinity of the small body. As shown in previous papers, it is possible to identify the initial conditions on the b-plane that lead to post-encounter orbits of given semimajor axis. In this paper we exploit analytical relationships between b-plane coordinates and pre-encounter orbital elements and compute the probability of transition to these post-encounter states, and numerically check the validity of the analytic approach.     

Ecological evaluation of an experimental beneficial use scheme for dredged sediment disposal in shallow tidal waters

An experiment was performed to test an alternative dredging strategy for the Westerschelde estuary. Clean sand dredged from the navigation channel was disposed seawards of an eroding intertidal flat in order to modify morphology and hydrodynamics, improving the multi-channel system with ecologically productive shallow water habitat. Five years of intensive monitoring revealed that part of the disposed sediment moved slowly towards the flat, increasing the very shallow subtidal and intertidal area, as planned. The sand in the impact zone became gradually finer after disposal, possibly due to reduced current velocities. Nevertheless, no changes in macrobenthic biomass, density, species richness and composition were detected in the subtidal zone, also demonstrating rapid macrobenthic recovery. In the intertidal zone, no ecological effects could be revealed superimposed on trends associated with long-term sediment fining. Thus, despite morphological success and absence of detected negative ecological impacts of the experiment, new beneficial habitat was not created.     

The Crati Submarine Fan, Ionian Sea

The Crati Fan is located in the tectonically active submerged extension of the Apennines chain and foretrough. The small fan system is growing in a relatively shallow (200 to 450 m), elongate nearshore basin receiving abundant input from the Crati River. The fan is characterized by a short, steep, channelized section (inner or upper fan) and a smooth, slightly bulging distal section (outer or lower fan). The numerous subparallel channels head in the shelf or littoral zone and do not form branching distributary patterns. Sand and mud depositional lobes of the outer fan stretch over more than 60% of fan length. Margin setting represents fan and/or source area