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Pokrovski G.S.,French National Center for Scientific Research | Dubessy J.,CNRS Georesources lab
Earth and Planetary Science Letters | Year: 2015

The interpretation of sulfur behavior in geological fluids and melts is based on a long-standing paradigm that sulfate, sulfide, and sulfur dioxide are the major sulfur compounds. This paradigm was recently challenged by the discovery of the trisulfur ion S3- in aqueous S-bearing fluids from laboratory experiments at elevated temperatures. However, the stability and abundance of this potentially important sulfur species remain insufficiently quantified at hydrothermal conditions. Here we used in situ Raman spectroscopy on model thiosulfate, sulfide, and sulfate aqueous solutions across a wide range of sulfur concentration (0.5-10.0 wt%), acidity (pH 3-8), temperature (200-500 °C), and pressure (15-1500 bar) to identify the different sulfur species and determine their concentrations. Results show that in the low-density (<0.2g/cm3) vapor phase, H2S is the only detectable sulfur form. By contrast, in the denser liquid and supercritical fluid phase, together with sulfide and sulfate, the trisulfur radical ion S3- is a ubiquitous and thermodynamically stable species from 200 °C to at least 500 °C. In addition, the disulfur radical ion S2- is detected at 450-500 °C in most solutions, and polymeric molecular sulfur with a maximum abundance around 300 °C in S-rich solutions. These results, combined with revised literature data, allow the thermodynamic properties of S3- to be constrained, enabling quantitative predictions of its abundance over a wide temperature and pressure range of crustal fluids. These predictions suggest that S3- may account for up to 10% of total dissolved sulfur (Stot) at 300-500 °C in fluids from arc-related magmatic-hydrothermal systems, and more than 50% Stot at 600-700 °C in S-rich fluids produced via prograde metamorphism of pyrite-bearing rocks. The trisulfur ion may favor the mobility of sulfur itself and associated metals (Au, Cu, Pt, Mo) in geological fluids over a large range of depth and provide the source of these elements for orogenic Au and porphyry-epithermal Cu-Au-Mo deposits. Furthermore, the ubiquity of S3- in aqueous sulfate-sulfide systems offers new interpretations of the kinetics and mechanisms of sulfur redox reactions at elevated temperatures and associated mass-dependent and mass-independent fractionation of sulfur isotopes. © 2014 Elsevier B.V. Source


Vigneresse J.-L.,CNRS Georesources lab
Geoscience Frontiers | Year: 2015

Abstract Felsic intrusions present ubiquitous structures. They result from the differential interactions between the magma components (crystal, melt, gas phase) while it flows or when the flow is perturbed by a new magma injection. The most obvious structure consists in fabrics caused by the interactions of rotating grains in a flowing viscous melt. New magma inputs through dikes affect the buk massif flow, considered as global within each mineral facies. A review of the deformation and flow types developing in a magma chamber identifis the patterns that could be expected. It determines their controlling parameters and summarizes the tools for their quantification. Similarly, a brief review of the rheology of a complex multi-phase magma identifies and suggests interactions between the different components. The specific responses each component presents lead to instability development. In particular, the change in vorticity orientation, associated with the switch between monoclinic to triclinic flow is a cause of many instabilities. Those are preferentially local. Illustrations include fabric development, shear zones and flow banding. They depend of the underlying rheology of interacting magmas. Dikes, enclaves, schlieren and ladder dikes result from the interactions between the magma components and changing boundary conditions. Orbicules, pegmatites, unidirectional solidification textures and miarolitic cavities result from the interaction of the melt with a gaseous phase. The illustrations examine what is relevant to the bulk flow, local structures or boundary conditions. In each case a field observation illustrates the instability. The discussion reformulates instability observations, suggesting new trails for ther description and interpretation in terms of local departure to a bulk flow. A brief look at larger structures and at their evolution tries to relate these instabilities on a broader scale. The helical structures of the Říčany pluton, Czech Republic and by the multiple granitic intrusions of Dolbel, Niger illustrate such events. © 2014 China University of Geosciences (Beijing) and Peking University. Source


This article presents a constitutive model for the elastic–plastic, viscoplastic and damage behaviour of hard porous rocks. The main hypotheses of the model are based on a large set of experimental data which are also presented in the paper. This constitutive model is of the over-stress type and is formulated within the unified theory of inelastic flow. An energy-based failure surface was considered to describe both short- and long-term behaviours within the same formulation. The inelastic yield surface is of static nature while the failure and damage surfaces are of dynamic nature. The kinetic law is written in terms of internal state variables that allow the description of how the frictional and the cohesive internal strengths of the material evolves. The reversible inelastic behaviour is also modelled using the “under-stress” concept, and considering that, it depends explicitly on the locked energy during the inelastic flow. In addition, this model is adapted to the porous nature of rocks such as iron ore that exhibit strong volumetric deformations and mean stress dependence. A large fraction of the volumetric straining is explained by damage mechanisms that also allow the accelerated creep to be modelled. Model parameters can easily be identified in the laboratory with commonly used mechanical tests. The constitutive model was implemented in a numerical code, and some qualitative simulations and comparisons with experimental curves showed the suitability of the model to reproduce both short- and long-term behaviours of porous rocks similar to iron ore. © 2014, Springer-Verlag Berlin Heidelberg. Source


Sevostianov I.,New Mexico State University | Giraud A.,CNRS Georesources lab
International Journal of Engineering Science | Year: 2013

The paper focuses on the reformulation of classical Maxwell's (1873) homogenization method for elastic composites. Maxwell's scheme that equates the far fields produced by a set of inhomogeneities and by a fictitious domain with unknown effective properties is re-written in terms of the compliance contribution tensors. Explicit formula for tensor of effective elastic compliances is derived for the case the ellipsoidal fictitious domain. The method is illustrated by four examples-material containing multiple identical spheroidal pores, material containing three families of inhomogeneities having different shapes and properties, material containing circular cracks that have preferential orientation with certain scatter, and material containing randomly oriented non-ellipsoidal (superspherical) pores. © 2013 Elsevier Ltd. All rights reserved. Source


Scholtes L.,CNRS Georesources lab | Donze F.-V.,Joseph Fourier University
Journal of the Mechanics and Physics of Solids | Year: 2012

The Discrete Element Method (DEM) is increasingly used to simulate the behavior of rock. Despite their intrinsic capability to model fracture initiation and propagation starting from simple interaction laws, classical DEM formulations using spherical discrete elements suffer from an intrinsic limitation to properly simulate brittle rock behavior characterized by high values of UCS/TS ratio associated with non-linear failure envelopes, as observed for hard rock like granite. The present paper shows that the increase of the interaction range between the spherical discrete elements, which increases locally the density of interaction forces (or interparticle bonds), can overcome this limitation. It is argued that this solution represents a way to implicitly take into account the degree of interlocking associated to the microstructural complexity of rock. It is thus shown that increasing the degree of interlocking between the discrete elements which represent the rock medium, in addition to enhancing the UCS/TS ratio, results in a non-linear failure envelop characteristic of low porous rocks. This approach improves significantly the potential and predictive capabilities of the DEM for rock modeling purpose. A special emphasis is put on the model ability to capture the fundamental characteristics of brittle rocks in terms of fracture initiation and propagation. The model can reproduce an essential component of brittle rock failure, that is, cohesion weakening and frictional strengthening as a function of rock damage or plastic strain. Based on model predictions, it is finally discussed that frictional strengthening may be at the origin of the brittle ductile transition occurring at high confining pressures. © 2012 Elsevier Ltd. All rights reserved. Source

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