Rare earth, major and trace elements in Jurassic manganese shales of the Northern Calcareous Alps: hydrothermal versus hydrogenous origin of stratiform manganese deposits

Summary ?The rare earth, major and trace element geochemistry of Jurassic deep marine manganese shales allow insight into their environment of deposition. We present data of 24 samples from the Northern Calcareous Alps (Eastern Alps), collected from Late Jurassic strata of the Tennengebirge and from Early Jurassic strata of the Karwendel Mts. Whereas major and trace element geochemistry is controlled by the detrital input, rare earth element data and the relationship between total organic carbon and (pyritic) sulfur can be used to constrain the origin of the manganese accumulation. The data of this study are compatible with a hydrogenous precipitation of manganese by strongly varying redox-conditions at the sediment–water interface of a slope basin. Received December 21, 2001; revised version accepted February 18, 2002     

Tephrochronology and tephrostratigraphy of two Pleistocene continental fossiliferous successions from central Italy

The stratigraphical context of two Middle Pleistocene fossiliferous palaeosols from Central Italy (Abruzzo and Tuscany) have been studied. Small mammals and molluscs occur in both palaeosols, which are covered by tephra layers that were analysed using an interdisciplinary approach. Application of fission‐track dating to apatites separated from the Case Picconetto tephra (Pescara, Abruzzo), yielded an age of 0.48 ± 0.04 Ma, indistinguishable from those previously determined for the Campani Quarry (Lower Valdarno, Tuscany) (0.46 ± 0.05 Ma and 0.48 ± 0.05 Ma). Geochemical and petrographic investigations indicate that these tephra originated from different volcanoes, the Alban Hills Volcanic Complex and the Vico Volcano (Latium) respectively. Small mammal and mollusc assemblages indicate different palaeoclimatic and palaeoenvironmental conditions for the Case Picconetto and Campani Quarry palaeosols. Warm and humid conditions can be inferred for the Campani Quarry site, whereas open and cold conditions can be inferred for Case Picconetto. On the basis of faunal data, fission‐track dates and attribution of tephra to specific volcanic eruptions, we suggest a correlation of these faunas with marine oxygen isotope stage 14 (Case Picconetto) and with marine oxygen isotope stage 11 (Campani Quarry), respectively. Copyright © 2003 John Wiley & Sons, Ltd.     

Bond rolling resistance and its effect on yielding of bonded granulates by DEM analyses

A discrete element modelling of bonded granulates and investigation on the bond effect on their behaviour are very important to geomechanics. This paper presents a two‐dimensional (2‐D) discrete element theory for bonded granulates with bond rolling resistance and provides a numerical investigation into the effect of bond rolling resistance on the yielding of bonded granulates. The model consists of mechanical contact models and equations governing the motion of bonded particles. The key point of the theory is that the assumption in the original bond contact model previously proposed by the authors (55th CSCE‐ASCE Conference, Hamilton, Ont., Canada, 2002; 313–320; J. Eng. Mech. (ASCE) 2005; 131 (11):1209–1213) that bonded particles are in contact at discrete points, is here replaced by a more reliable assumption that bonded particles are in contact over a width. By making the idealization that the bond contact width is continuously distributed with the normal/tangential basic elements (BE) (each BE is composed of spring, dashpot, bond, slider or divider), we establish a bond rolling contact model together with bond normal/tangential contact models, and also relate the governing equations to local equilibrium. Only one physical parameter β needs to be introduced in the theory in comparison to the original bond discrete element model. The model has been implemented into a 2‐D distinct element method code, NS2D. Using the NS2D, a total of 86 1‐D, constant stress ratio, and biaxial compressions tests have been carried out on the bonded granular samples of different densities, bonding strengths and rolling resistances. The numerical results show that: (i) the new theory predicts a larger internal friction angle, a larger yielding stress, more brittle behaviour and larger final broken contact ratio than the original bond model; (ii) the yielding stress increases nonlinearly with the increasing value of β, and (iii) the first‐yield curve (initiation of bond breakage), which define a zone of none bond breakage and which shape and size are affected by the material density, is amplified by the bond rolling resistance in analogous to that predicted by the original bond model. Copyright © 2006 John Wiley & Sons, Ltd.     

Modelling of deformation response and chemo‐mechanical coupling in chalk

A constitutive relation is derived for describing the mechanical response of chalk. The approach is based on a phenomenological framework which employs chemo‐plasticity. The properties of the material are assumed to be affected by the physico‐chemical processes that occur through the interaction between the skeleton and the pore fluid. The underlying mechanism is discussed by invoking a micromechanical analysis. The performance of the framework is illustrated by examining the evolution of mechanical characteristics in the presence of different pore fluids. Copyright © 2006 John Wiley & Sons, Ltd.     

A major sulphur isotope event at c. 510 Ma: a possible anoxia–extinction–volcanism connection during the Early–Middle Cambrian transition?

A new approach to constraining seawater δ³⁴S and sulphate concentration using francolite‐bound sulphate reveals an abrupt increase in δ³⁴S to +50‰ around the Early–Middle Cambrian boundary. Such high δ³⁴S values are best explained by increased rates of pyrite burial due to ocean anoxia coupled with an increased sensitivity of the ocean sulphate reservoir to perturbations due to low sulphate concentrations of 500–700 μgL^?1. We argue that the spread of anoxic waters at this time was partly the result of greenhouse warming related to the eruption of the Kalkarindji Large Igneous Province of northern Australia and that it triggered the collapse of early metazoan reef ecosystems during the latest Early Cambrian. Mass extinctions of the last 260 Myr have all coincided with enhanced volcanic activity, while several are also associated with positive shifts in seawater δ³⁴S. Extending this correlation back in time further implicates volcanically induced climate change as a major determining factor in biosphere evolution. Terra Nova, 18, 257–263, 2006     

Chemical alteration of tephra in the depositional environment: theoretical stability modelling

The study of the chemical stability of vitreous material in aqueous media is well‐established. There has to date been little consideration of the implications of variations in the chemical durability of tephra in Quaternary tephrochronology. Chemical alteration can take the form of cationic leaching from the matrix, or complete destruction of the silica network, either of which could constrain the ability to chemically identify distal tephra. Here we apply established models of vitreous durability to the published chemical analyses of a large number of Icelandic tephras in order to predict their relative durabilities under equivalent conditions. This suggests that some important tephras have relatively poor chemical stability, and that rhyolitic tephras are, in general, more stable than basaltic. We conclude that tephras should be expected to show predictable differential chemical stability in the post‐depositional environment. Copyright © 2003 John Wiley & Sons, Ltd.     

A multi‐level parallelized substructuring‐frontal solution for coupled thermo/hydro/mechanical problems in unsaturated soil

This paper proposes a multi‐level parallelized substructuring–frontal combined algorithm for the analysis of the problem of thermo/hydraulic/mechanical behaviour of unsaturated soil. Temperature, displacement, pore water pressure and pore air pressure are treated as the primary variables in a non‐linear analysis. Details are given firstly of the substructuring–frontal combined approach. The incorporation of the algorithm in a multi‐level parallel strategy is then discussed. The parallel processing can thus be carried out at different substructural levels. The method thus developed impacts, in a positive way, on both computer storage requirement and execution time. Copyright © 2003 John Wiley & Sons, Ltd.     

Microtextures and crystal chemistry in P21/c pigeonites

Summary ?A single-crystal X-ray investigation was performed on crystals of P2₁/c natural pigeonite with varying Ca and Fe^* ( = Fe²⁺ + Mn²⁺) contents, in order to verify the effect of microtextural disorder on structure refinements and to constrain the crystal chemistry of pigeonite. Antiphase domains and exsolution lamellae affect differently the refinement results. In a crystal free of exsolution the structure obtained after refinement with all reflections is an average of that of the antiphase domains and of their boundaries, whereas in an exsolved crystal it represents only the structure of the prevailing pigeonite lamellae. The refinement using only h + k odd reflections seems to give the structure of the Ca-free pigeonite characteristic of the antiphase domains rather than that of Ca-rich domain walls. The ratio of the scale factors in refinements with all reflections and with only h + k odd reflections allows the ratios of the exsolved augite and pigeonite phases to be estimated. The crystal chemistry of the investigated samples follows the trends outlined by data on Ca-free and Fe-free synthetic samples. In particular, it is shown that Ca and Fe^* substitution for Mg induce similar changes in the average structure, i.e. both induce an expansion in the M1 polyhedron and decrease the difference between the M2–O3 distances. Received October 18, 2001; revised version accepted February 15, 2002     

Ionprobe U-Pb zircon ages from the high-pressure/low-temperature mélange of Syros, Greece: age diversity and the importance of pre-Eocene subduction

The Cycladic blueschist belt in the central Aegean Sea has experienced high‐pressure (HP) metamorphism during collisional processes between the Apulian microplate and Eurasia. The general geological and tectonometamorphic framework is well documented, but one aspect which is yet not sufficiently explored is the importance of HP mélanges which occur within volcano‐sedimentary successions. Unresolved issues concern the range in magmatic and metamorphic ages recorded by mélange blocks and the significance of eventual pre‐Eocene HP metamorphism. These aspects are here addressed in a U‐Pb zircon study focusing on the block–matrix association exposed on the island of Syros. Two gneisses from a tectonic slab of this mélange, consisting of an interlayered felsic gneiss‐glaucophanite sequence, yielded zircon ²⁰⁶Pb/²³⁸U ages of 240.1 ± 4.1 and 245.3 ± 4.9 Ma, respectively, similar to Triassic ages determined on zircon in meta‐volcanic rocks from structurally coherent sequences elsewhere in the Cyclades. This strongly suggests that parts of these successions have been incorporated in the mélanges and provides the first geochronological evidence that the provenance of mélange blocks/slabs is neither restricted to a single source nor confined to fragments of oceanic lithosphere. Zircon from a jadeitite and associated alteration zones (omphacitite, glaucophanite and chlorite‐actinolite rock) all yielded identical ²⁰⁶Pb/²³⁸U ages of c. 80 Ma. Similar Cretaceous U‐Pb zircon ages previously reported for mélange blocks have been interpreted by different authors to reflect magmatic or metamorphic ages. The present study adds a further argument in favour of the view that zircon formed newly in some rock types at c. 80 Ma, due to hydrothermal or metasomatic processes in a subduction zone environment, and supports the interpretation that the Cycladic blueschist belt records both Cretaceous and Eocene HP episodes and not only a single Tertiary HP event.     

Size and shape evolution of pores in a viscoplastic matrix under compression

The frequent use of soils and earth materials for hydraulic capping and for geo‐environmental waste containment motivated our interest in detailed modelling of changes in size and shape of macro‐pores to establish links between soil mechanical behaviour and concurrent changes in hydraulic and transport properties. The objective of this study was to use finite element analysis (FEA) to test and extend previous analytical solutions proposed by the authors describing deformation of a single macro‐pore embedded in linear viscoplastic soil material subjected to anisotropic remote stress. The FEA enables to consider more complex pore geometries and provides a detailed picture of matrix yield behaviour to explain shortcomings of approximate analytical solutions. Finite element and analytical calculations agreed very well for linear viscous as well as for viscoplastic materials, only limited for the case of isotropic remote stress due to the simplifications of the analytical model related to patterns and onset of matrix‐yielding behaviour. FEA calculations were compared with experimental data obtained from a compaction experiment in which pore deformation within a uniform modelling clay sample was monitored using CAT scanning. FEA predictions based on independently measured material properties and initial pore geometry provided an excellent match with experimentally determined evolution of pore size and shape hence lending credence to the potential use of FEA for more complex pore geometries and eventually connect macro‐pore deformation with hydraulic properties. Copyright © 2006 John Wiley & Sons, Ltd.