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.     

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.     

Assessing catchment-scale spatial and temporal patterns of groundwater and stream salinity

Understanding catchment-scale patterns of groundwater and stream salinity are important in land- and water-salinity management. A large-scale assessment of groundwater and stream data was undertaken in the eastern Mt Lofty Ranges of South Australia using geographical information systems (GIS), regional scale hydrologic data, hydrograph separation and hydrochemical techniques. Results of the study show: (1) salts were mostly of marine origin (75%), while sulfate and bicarbonate from mineral weathering comprised most of the remainder, (2) elevated groundwater salinities and stable water isotopic compositions similar to mean rainfall indicated that plant transpiration was the primary salt accumulation mechanism, (3) key factors explaining groundwater salinity were geology and rainfall, with overall catchment salinity inversely proportional to average annual rainfall, and groundwater salinity ‘hotspots’ (EC >8 mS/cm) associated with geological formations comprising sulfidic marine siltstones and shales, (4) shallow groundwater correlated with elevated stream salinity, implying that baseflow contributed to stream salt loads, with most of the annual salt load (estimated to be 24,500 tonnes) occurring in winter when baseflow volume was highest. Salt-load analysis using stream data could be a practical, low-cost technique to rapidly target the investigation of problem areas within a catchment.     

Tomographic joint inversion of first arrivals in a real case fromSaudi Arabia

A joint inversion of both first and refracted arrivals is applied on a seismic line, acquired onshore, in order to obtain a well‐resolved velocity field for the computation of static corrections. The use of different arrivals in the inversion involves exploiting the information derived from the different raypaths associated with each wave type, thus enhancing the reliability of the inversion. The data was gathered by Saudi Aramco in an area of the Arabian Peninsula characterized by strong lateral variations, both in topography and shallow velocity, and where therefore a well‐defined near‐surface velocity field is important. In addition to velocity, the depth distribution of the quality factor Q is computed from the tomographic inversion of the seismic‐signal frequency shift. Thus, the Q‐factor field is used to perform an inverse Q‐data filtering and improve the resolution of the final stacked section.     

Conceptually-based shot noise modeling of streamflows at short time interval

A conceptual-stochastic approach to short time runoff data modelling is proposed, according to the aim of reproducing the hydrological aspects of the streamflow process and of preserving as much as possible the dynamics of the process itself. This latter task implies preservation of streamflow characteristics at higher scales of aggregation and, within a conceptual framework, involves compatibility with models proposed for the runoff process at those scales. At a daily time scale the watershed response to the effective rainfall is considered as deriving from the response of three linear reservoirs, respectively representing contributions to streamflows of large deep aquifers, with over-year response lag, of aquifers which run dry by the end of the dry season and of subsurface runoff. The surface runoff component is regarded as an uncorrelated point process. Considering the occurrences of effective rainfall events as generated by an independent Poisson process, the output of the linear system represents a conceptually-based multiple shot noise process. Model identification and parameter estimation are supported by information related to the aggregated runoff process, in agreement to the conceptual framework proposed, and this allows parameter parsimony, efficient estimation and effectiveness of the streamflow reproduction. Good performances emerged from the model application and testing made with reference to some daily runoff series from Italian basins.     

Sulfide composition and phase relations in the Fe-Ni-Cu ore deposits of the Ivrea-Verbano basic complex (western Alps,Italy)

The bulk composition, mineralogy and mineral chemistry of base-metal sulfides have been investigated in the Fe-Ni-(Cu) ore deposits of the Ivrea-Verbano basic complex.The sulfide ores mostly display textural evidence of having been primarily deposited as an immiscible melt. Bulk compositions of the ores indicate that considerably low Ni/Fe and Ni/Co ratios are found in deposits developed close to metasedimentary country rocks, possibly as a result of mixing with sedimentary sulfur.Phase relations of primary sulfides indicate that early crystallization of the ore was dominated by a monosulfide solid solution (Mss) with a pyrrhotite composition, from which pentlandite and chalcopyrite were formed through subsolidus exsolution. Pentlandite from contaminated ores is typically enriched in Co. Troilite and hexagonal intermediate pyrrhotite intergrowths frequently occur due to low-temperature equilibration of metal-rich pyrrhotites, suggesting a low S fugacity of the original sulfide melt.The sulfides may be locally mobilized and redeposited along shear zones within the same host rock, giving rise to fairly massive ores having a typical cemented-breccia texture. Bulk composition and assemblages suggest that mobilization occurred at various temperatures during the cooling history of the ore, when sulfides were still in the molten state or at a lower temperature under the influence of abundant deuteric fluids. In this last case, growth of pyrite is seen as being possibly due to sulfurization and/or oxidation.     

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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Datation UPb sur zircons des dolérites tholéiitiques pyrénéennes (ophites) à la limite Trias–Jurassique et relations avec les tufs volcaniques dits « infra-liasiques » nord-pyrénéens

The tholeiitic doleritic magmatism (ophites) in the Aspe valley of the Pyrenees has been dated on the Triassic–Jurassic boundary (199±2 Ma) by the UPb method on zircon (SHRIMP). Emplacement of the ophites was probably synchronous with that of the earliest ‘Infraliassic’ Ségalas tuffs. The ophites are thus related to the Central Atlantic Magmatic Province (CAMP) whose emplacement linked with the fracturing of Pangea, preceded the opening of the Atlantic Ocean. To cite this article: P. Rossi et al., C. R. Geoscience 335 (2003).     

Characterization of wrench tectonics from dating of syn- to post-magmatism in the north-western French Massif Central

This work establishes the relative timing of pluton emplacement and regional deformation from new dating and structural data. (1) Monazite and (2) zircon dating show Tournaisian ages for the Guéret granites [Aulon granite 352 ± 5 Ma (1), 351 ± 5 Ma (2) and Villatange tonalite 353 ± 6 Ma (1)] and Viseo-Namurian ages for the north Millevaches granites [Chavanat granite 336 ± 4 Ma (1), Goutelle granite 336 ± 3 Ma (1), Royère granite 323 ± 2 Ma (1) and 328 ± 6 Ma (2), Courcelles granite 318 ± 3 Ma (1)]. The Guéret and Millevaches granites are separated by the N110 Arrènes–la Courtine Shear Zone (ACSZ), composed from West to East by the Arrènes Fault (AF), the North Millevaches Shear Zone (NMSZ) and the la Courtine Shear Zone (CSZ), respectively. Tournaisian Guéret granites experienced a non-coaxial dextral shearing (NMSZ) recorded by the Villatange granite while the Aulon granite (Guéret granite) cuts across this dextral shear zone which thus stopped shearing during Tournaisian time. Visean to Namurian Millevaches granites experienced a coaxial deformation. Therefore, low displacements along the NMSZ and the CSZ occurred at the emplacement time of Chavanat and Pontarion-Royère granites (336–323 Ma). The structural analyses of Goutelle granite emphasizes a deformation related to the dextral Creuse Fault System (CFS) oriented N150–N160. From 360 to 300 Ma, the Z strain axis is always horizontal inferring a wrench setting for these granite emplacements. During this tectonic evolution, the Argentat zone acted as a minor normal fault and is related with a local Middle Visean (340–335 Ma) syn-orogenic extension on the western border of the Millevaches massif.     

Transaction links through cities: ‘decision cities’ and ‘service cities’ in outsourcing by leading Brazilian firms

Most world city studies focus on where the provision of advanced producer services takes place, but in this study the location of the service clients are also taken into account. Production-service transactions are identified as links between ‘service city’ and ‘decision city’ (client HQ) and classified as intra-city (where a firms uses local (same city) services) and inter-city which may be domestic or foreign depending on whether the client uses services in or out of the country. Sampling the leading firms in Brazil, 218 transaction links are described and analysed in terms of cities, firm sectors, ownership and market. The analyses are used to inform a rereading of gateway city functions that takes into account the concentration/dispersal nexus in economic globalization. Thus, whereas the dominance of Sao Paulo in the Brazilian economy is confirmed, this is not interpreted as a simple gateway function with this one city ‘articulating’ the national economy into the world economy. A much more complex situation is revealed with by-passing of the gateway also much in evidence. The conclusion is that this shows concentration and dispersion of economic activity happening simultaneously in Brazil.