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.     

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.     

Descriptors of impulsive signal levels commonly used in underwateracoustics

Impulsive acoustic waveforms are characterized by a different set of derived quantities than are continuous waveforms. This note presents commonly accepted definitions, units, and symbols used to describe the magnitude of impulsive underwater signals     

Generalized strain probing of constitutive models

Advanced material constitutive models are used to describe complex soil behaviour. These models are often used in the solution of boundary value problems under general loading conditions. Users and developers of constitutive models need to methodically investigate the represented soil response under a wide range of loading conditions. This paper presents a systematic procedure for probing constitutive models. A general incremental strain probe, 6D hyperspherical strain probe (HSP), is introduced to examine rate‐independent model response under all possible strain loading conditions. Two special cases of HSP, the true triaxial strain probe (TTSP) and the plane‐strain strain probe (PSSP), are used to generate 3‐D objects that represent model stress response to probing. The TTSP, PSSP and general HSP procedures are demonstrated using elasto‐plastic models. The objects resulting from the probing procedure readily highlight important model characteristics including anisotropy, yielding, hardening, softening and failure. The PSSP procedure is applied to a Neural Network (NN) based constitutive model. It shows that this probing is especially useful in understanding NN constitutive models, which do not contain explicit functions for yield surface, hardening, or anisotropy. Copyright © 2004 John Wiley & Sons, Ltd.     

Theoretical accuracy of synthetic aperture sonar micronavigation using a displaced phase-center antenna

The Cramer-Rao lower bounds on the cross-track translation and rotation of a displaced phase-center antenna (DPCA) in the slant range plane between two successive pings (known as DPCA sway and yaw in what follows) are computed, assuming statistically homogeneous backscatter. These bounds are validated using experimental data from a 118-182-kHz sonar, showing an accuracy of the order of 20 microns on the ping-to-ping cross-track displacements. Next, the accuracy required on the DPCA sway and yaw in order to achieve a given synthetic aperture sonar (SAS) beampattern specification, specified by the expected SAS array gain, is computed as a function of the number P of pings in the SAS. Higher accuracy is required when P increases to counter the accumulation of errors during the integration of the elementary ping-to-ping estimates: the standard deviation must decrease as P/sup -1/2/ for the DPCA sway and P/sup -3/2/ for the yaw. Finally, by combining the above results, the lower bounds on DPCA micronavigation accuracy are established. These bounds set an upper limit to the SAS length achievable in practice. The maximum gain Q in cross-range resolution achievable by a DPCA micronavigated SAS is computed as a function of the key SAS parameters. These theoretical predictions are compared with simulations and experimental results.     

Metamorphism in Archaean greenstone belts: calculated fluid compositions and implications for gold mineralization

An inescapable consequence of the metamorphism of greenstone belt sequences is the release of a large volume of metamorphic fluid of low salinity with chemical characteristics controlled by the mineral assemblages involved in the devolatilization reactions. For mafic and ultramafic sequences, the composition of fluids released at upper greenschist to lower amphibolite facies conditions for the necessary relatively hot geotherm corresponds to those inferred for greenstone gold deposits (X_CO2= 0.2–0.3). This result follows from the calculation of mineral equilibria in the model system CaO–MgO–FeO–Al₂O₃–SiO₂–H₂O–CO₂, using a new, expanded, internally consistent dataset. Greenstone metamorphism cannot have involved much crustal over-thickening, because very shallow levels of greenstone belts are preserved. Such orogeny can be accounted for if compressive deformation of the crust is accompanied by thinning of the mantle lithosphere. In this case, the observed metamorphism, which was contemporaneous with deformation, is of the low-P high-T type. For this type of metamorphism, the metamorphic peak should have occurred earlier at deeper levels in the crust; i.e. the piezothermal array should be of the ‘deeper-earlier’type. However, at shallow crustal levels, the piezothermal array is likely to have been of ‘deeper-later’type, as a consequence of erosion. Thus, while the lower crust reached maximum temperatures, and partially melted to produce the observed granites, mid-crustal levels were releasing fluids prograde into shallow crustal levels that were already retrograde. We propose that these fluids are responsible for the gold mineralization. Thus, the contemporaneity of igneous activity and gold mineralization is a natural consequence of the thermal evolution, and does not mean that the mineralization has to be a consequence of igneous processes. Upward migration of metamorphic fluid, via appropriate structurally controlled pathways, will bring the fluid into contact with mineral assemblages that have equilibrated with a fluid with significantly lower X_CO2. These assemblages are therefore grossly out of equilibrium with the fluid. In the case of infiltrated metabasic rocks, intense carbonation and sulphidation is predicted. If, as seems reasonable, gold is mobilized by the fluid generated by devolatilization, then the combination of processes proposed, most of which are an inevitable consequence of the metamorphism, leads to the formation of greenstone gold deposits predominantly from metamorphic fluids.     

Dissolution and depletion of ferromagnesian minerals from Holocene tephra layers in an acid bog,New Zealand,and implications for tephra correlation

This study examines the depletion of ferromagnesian silicate minerals from a sequence of thin, distal, mainly rhyolitic tephra layers of Holocene age preserved in an acid peat bog (Kopouatai), North Island, New Zealand. The rate of such depletion has been fast, as indicated by the complete loss of biotite from one tephra layer (Kaharoa Tephra), in which it is normally dominant, in only ca. 770 yr. Chemical dissolution is advocated as the likely cause for the depletion, with amphiboles and other mineral grains commonly showing etch pits, microcaves, and other characteristic surface solution features. Theoretical thermodynamic and kinetic models show a marked increase in the rate of dissolution of all ferromagnesian minerals under conditions of low pH (< 4), but that where silica concentrations in solution are high the relative proportions of minerals remaining are unaffected. However, where concentrations of dissolved silica are low, as in most bog environments, the relative proportions of ferromagnesian minerals are affected as well as absolute amounts being decreased. Amphiboles are depleted relative to pyroxenes, consistent with kinetic studies. The results show that the identification and correlation of tephras on the basis of relative abundances of ferromagnesian minerals alone may be unreliable, and emphasise the need to use multiple criteria in such studies.