Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A reactive percolation experiment was conducted by injecting seawater into a permeable olivine aggregate at 190 °C and 19 MPa to explore the relationships between hydration reactions and hydrodynamic properties during the onset of serpentinization in the ultramafic lithosphere exposed at mid-ocean ridges. The experiment was stopped after 23 days when the sample became impermeable. The initial flow rate was 0.2 mL/h and then was decreased down to 0.06 mL/h after 8 days. Permeability decreased continuously throughout the experiment. The analyses of fluid chemistry time series and of the mineralogy and structure of the reacted sample showed olivine dissolution and precipitation of proto-serpentine, brucite and Fe-oxides. These reactions are controlled by coupled hydrodynamic and chemical processes interacting at different time and spatial scales. Their first characteristic is the production of silica rich outlet fluids in disequilibrium with the observed reacted mineral assemblages. These compositions are interpreted as resulting from a suite of coupled dissolution-precipitation reactions, controlled at the pore scale by surface kinetic processes, that rapidly reaches steady-state (constant fluid composition independent of fluid flux). Hence, the effective rate of serpentinization was controlled, to the first order, by the transport of reactants during the experiment. Mass balance calculations show that the rate of olivine conversion was fast (0.2-0.5 wt%/day), yet only ∼8 wt% of the olivine sample reacted, because the permeability drop limited fluid circulation. Porosity varied little during the experiment compared to permeability changes: the decrease of permeability was explained by the structure of the newly formed serpentine favouring the clogging of fluid paths. The rate at which permeability decreased was the fastest at low flux conditions. This suggests that permeability changes were not controlled simply by the kinetics of the serpentinization reactions, but mainly reflected the development of low Peclet pore scale zones forming micro-environments that control the serpentinization reaction-paths. These results outline the need to take into account the coupling of hydrodynamic and chemical processes when modelling the effects of reactive transport within the hydrating oceanic lithosphere.
ISSN: 0012-821X

hal-00855043
https://hal.archives-ouvertes.fr/hal-00855043
DOI : 10.1016/j.epsl.2013.03.052

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A set of four reactive flow-through experiments at temperature T = 100 degrees C and total pressure P=12 MPa was performed in limestone reservoir samples. By using various ranging from 0.7 to 10 MPa, these experiments mimic mass transfers occurring (1) near the injection well, where the brine is almost saturated with CO2 (i.e. P-CO2 approximate to P), and (2) at increasing distances from the injection well, where the fluid displays lower values and higher divalent cation concentrations due rock dissolution along the fluid pathway. Results for P-CO2 = 10 MPa show non-uniform dissolution features associated with transport-controlled mass transfer, while reaction-controlled uniform dissolution is observed for P-CO2 = 2.5 MPa. The experiment with P-CO2 = 6 MPa allows investigating in detail the transition from transport-to reaction-controlled dissolution. Conversely, the experiment reproducing conditions far from the injection well (P-CO2 = 0.7 MPa), shows a decrease of porosity triggered by the precipitation of Mg-rich calcite. For all the dissolution experiments, the time-resolved porosity phi(t) can be modeled by a simple non-linear equation including parameters that characterise the dissolution regime triggered by the reactivity of the inlet fluid (measured by the Damkohler number, Da). Furthermore, all dissolution experiments display power scaling between permeability (k) and porosity (phi) with distinctly different scaling exponents characterising the reactivity of the fluid percolating the sample, independently from the decrease with time of the reactive surface area. It is shown also that dissolution at moderate positive values of Da seems the most efficient to increase permeability and promote a rapid spreading of the reaction front, while inducing minimal modification of the porosity in the vicinity of the CO2 injection well. These results can be used to parameterize the k-phi function for modeling the earliest dissolution processes occurring in the vicinity of the reaction front.
ISSN: 0009-2541

hal-00445277
https://hal.archives-ouvertes.fr/hal-00445277
DOI : 10.1016/j.chemgeo.2009.03.028

Éditeur(s) : HAL CCSD Oxford University Press (OUP): Policy B - Oxford Open Option A Oxford University Press (OUP)
Résumé : International audience
Peridotite xenoliths exhumed by Quaternary alkaline magmatism in the Tahalgha district, southern Hoggar, represent fragments of the subcontinental lithospheric mantle beneath the boundary between the two major structural domains of the Tuareg Shield: the ‘Polycyclic Central Hoggar’ to the east and the ‘Western Hoggar’, or ‘Pharusian Belt’, to the west. Samples were collected from volcanic centres located on both sides of a major lithospheric shear zone at 4°35' separating these two domains. Although showing substantial variations in their deformation microstructures, equilibrium temperatures and modal and chemical compositions, the studied samples do not display any systematic changes of these features across the 4°35' fault. The observed variations rather record small-scale heterogeneities distributed throughout the study area and reflecting the widespread occurrence of vein conduits and metasomatized wall-rocks related to trans-lithospheric melt circulation during the Cenozoic. These features include partial annealing of pre-existing deformation microstructures, post-deformation metasomatic reactions, and trace-element enrichment, coupled with heating from 750–900°C (low-temperature lherzolites) to 900–1150°C (intermediate-T lherzolites and high-T harzburgites and wehrlites). Trace-element modelling confirms that the range of rare earth element (REE) variations observed in the Tahalgha clinopyroxenes may be accounted for by reactive porous flow involving a single stage of basaltic melt infiltration into a light REE (LREE)-depleted protolith. Whole-rock compositions record the final entrapment of disequilibrium metasomatic melts upon thermal relaxation of the veins–wall-rock system. The striking correlations between equilibrium temperatures and trace-element enrichment favor a scenario in which the high-temperature peridotites record advective heat transport along melt conduits, whereas the intermediate- and low-temperature lherzolites reflect conductive heating of the host Mechanical Boundary Layer. This indicates that the lithosphere did not reach thermal equilibrium, suggesting that the inferred heating event was transient and was rapidly erased by thermal relaxation down to the relatively low-temperature present-day geotherm. The low-T (<900°C) deformed lherzolites (porphyroclastic to equigranular) are characterized by only incipient annealing and LREE-depleted clinopyroxene compositions. They were only weakly affected by the Cenozoic events and could represent relatively well-preserved samples from rejuvenated Pan-African lithosphere. Extensive lithospheric rejuvenation occurred either regionally during the Pan-African orogeny, as a result of lithospheric delamination or thermomechanical erosion after thickening, or more locally along the meridional shear zones. The low-T Tahalgha lherzolites are comparable with lherzolites from Etang de Lherz, southern France, interpreted as lithospheric mantle rejuvenated by melt-induced refertilization during a late stage of the Variscan orogeny.
ISSN: 0022-3530

hal-01107410
https://hal.archives-ouvertes.fr/hal-01107410
DOI : 10.1093/petrology/egu056

Éditeur(s) : HAL CCSD Elsevier
Résumé : The correct characterization of the effective reactive transport dynamics is an important issue for modeling reactive transport on the Darcy scale, specifically in situations in which reactions are localized, that is when different reactions occur in different portions of the porous medium. Under such conditions the conventional approach of homogenizing only the porous medium chemistry is not appropriate. We consider here reactive transport in a porous medium that is characterized by mass transfer between a mobile and a distribution of immobile regions. Chemical and physical heterogeneities are reflected by distributions of kinetic reaction rate constants and residence times in the immobile zones. We derive an effective reactive transport equation for the mobile solute that is characterized by non-local physical mass transfer and reaction terms. Specifically, chemical heterogeneity is upscaled in terms of a reactive memory function that integrates both chemical and physical heterogeneity. Mass transfer limitations due to physical heterogeneity yield effective kinetic rate coefficients that can be much smaller than the volumetric average of the local scale coefficients. These results help to explain and quantify the often reported discrepancy between observed field reaction rate constants and the ones obtained under well mixed laboratory conditions. Furthermore, these results indicate that transport under physical and chemical heterogeneity cannot be upscaled separately.
ISSN: 0169-7722

hal-00617674
https://hal.archives-ouvertes.fr/hal-00617674
DOI : 10.1016/j.jconhyd.2010.06.002

Éditeur(s) : HAL CCSD Nature Publishing Group
Résumé : International audience
Carbon is transported from Earth's surface into its interior at subduction zones. Carbonates in sediments overlying hydrothermally altered rocks (including serpentinites) within the subducted slab are the main carriers of this carbon1. Part of the carbon is recycled back to the surface by volcanism, but some is transferred to the deep Earth1, 2. Redox transformations during shallow subduction control the transfer and long-term fate of carbon, but are poorly explored1, 3. Here we use carbon stable isotopes and Raman spectroscopy to analyse the reduction of carbonate in an exhumed serpentinite-sediment contact in Alpine Corsica, France. We find that highly crystalline graphite was formed during subduction metamorphism and was concentrated in the sediment, within a reaction zone in direct contact with the serpentinite. The graphite in this reaction zone has a carbon isotopic signature (δ13C) of up to 0.8±0.1‰, similar to that of the original calcite that composed the sediments, and is texturally associated with the calcium-bearing mineral wollastonite that is also formed in the process. We use mass-balance calculations to show that about 9% of the total carbonaceous matter in the sedimentary unit results from complete calcite reduction in the reaction zone. We conclude that graphite formation, under reducing and low-temperature conditions, provides a mechanism to retain carbon in a subducting slab, aiding transport of carbon into the deeper Earth.
ISSN: 1752-0894

hal-00903464
https://hal.archives-ouvertes.fr/hal-00903464
DOI : 10.1038/NGEO1827

Éditeur(s) : HAL CCSD
Résumé : Geological storage of CO2 is one of diverse technologies being explored to reduce atmospheric carbon fromindustrial processes (i.e. fossil fuel combustion). One of the specific features of CO2 injection is the possibility ofgeochemical reactions (dissolution – precipitation) between mobile reactive brine (e.g. formation water enrichedin CO2) and the host rock during the spatial and temporal evolution of CO2. That leads to modifications in thepore structure, which in turn change the flow dynamics of the reservoir (e.g. the permeability k). Then, thesesstructural modifications can largely control the injectivity, so that the pressure field in the reservoir and also theCO2 propagation. Accordingly, it is crucial to explore the changes in the reservoir properties (e.g. structural andhydrodynamic) induced during a CO2 injection and specially the relationships between them (e.g. k or reactivesurface-Sr versus porosity-φ , k versus rock heterogeneity), for developing predictive modelling tools of thetransport and reaction processes occurring during a CO2 injection and reliable risk assessment. In the case ofcarbonate rocks, the application of the predictive models of transport and reaction is still challenging, because oftheir high heterogeneity so that the incertitude in the reaction kinetics of carbonate minerals.From this perspective, we realized brine-enriched in CO2 percolation experiments through carbonate rocksamples in thermodynamic conditions expected during CO2 injection in deep reservoirs (T = 100°C et P =12MPa). The permeability changes k(t) is monitored during the experiments and the porosity variationφ (t) iscalculated from chemical analyses of the sampled outlet fluids, using ICP-EAS. The pore structure modificationsare investigated from high resolution X ray micro tomography images acquired from the synchrotron ofGrenoble (ESRF). Depending to the dissolution regime, controlled by the reservoir rock fabric and the chemicalcomposition of the brine (e.g. PCO2), we observed that a modification of pore structure can either improve(atypical result in dissolution context) or impair the value of the permeability k.
Le stockage géologique du CO2 est l’une des diverses technologies étant explorées afin deréduire les émissions de carbone atmosphérique des processus industriels (i.e. combustion del’énergie fossile). L’une des spécifiques caractéristiques de l’injection du CO2 en profondeurreste la possibilité de réactions géochimiques (dissolution-précipitation) entre la saumureréactive mobile (e.g. eau de formation enrichie en CO2) et la roche encaissante durantl’évolution spatiale et temporelle du CO2, conduisant à des modifications dans la structure despores et par conséquent dans les propriétés d’écoulement du réservoir (e.g. la perméabilité k).Donc, ces changements structuraux peuvent largement contrôler l’injectivité, ainsi que lechamp de pression dans le réservoir et aussi la propagation du CO2. Il demeure ainsi cruciald’explorer les changement dans les propriétés de réservoirs (e.g. structurales ethydrodynamiques) induits durant une injection de CO2 et explicitement les relations existantesentre eux (e.g. k ou surface réactive-Sr versus porosité-φ , k versus hétérogénéité de la roche),afin de développer des outils de modélisation prédictive des processus de transport etréactionnels se produisant durant une injection de CO2 et d’évaluer de façon fiable les risques.Dans le cas des réservoirs carbonatés, l’application des modèles prédictifs de transport réactifdemeure toujours un enjeu, car contrainte par la forte hétérogénéité en leur sein ainsi que parl’incertitude dans la cinétique de réactions des minéraux carbonatés dans ce contexte. Danscette optique, nous avons réalisé des expériences de percolation à travers des échantillons deroches carbonatées dans les conditions thermodynamiques de stockage en profondeur (T =100°C et P =12 MPa). L’évolution de la perméabilité k(t) est suivie au cours desexpériences ; et la variation de la porosité φ (t) est calculée à partir des résultats d’analyseschimiques au ICP-AES des fluides de sortie échantillonnés. L’investigation des modificationsapportées à la structure des pores est réalisée par le biais de la Micro-Tomographie hauterésolution à rayon X, acquise au synchrotron de Grenoble (e.g. ESRF).Dépendant du régime de dissolution, contrôlé par la fabrique de la roche réservoir et lacomposition chimique de la saumuré chargée en CO2 (e.g. PCO2 engagée), on a observéqu’une modification de la structure de la roche peut soit améliorer soit détériorer (résultatatypique en contexte de dissolution) la valeur de la perméabilité k.
https://hal.archives-ouvertes.fr/tel-01142136

tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136/document
https://hal.archives-ouvertes.fr/tel-01142136/file/thesemangane2013.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study analyses the interactions between deformation and reactive fluid and melt percolation, and their effects on sub-arc mantle seismic properties based on microstructural observations on mantle xenoliths extracted by the Tubaf and Edison seamounts close to the Lihir Island, in the Papua New Guinea archipelago. These xenoliths sample an oceanic lithosphere, which has experienced high-temperature deformation in the presence of fluids or melts. This was followed by metasomatism under static conditions. Syn-kinematic percolation of reactive Si-rich melts or fluids in peridotites has produced pyroxene-enrichment, grain size reduction, and dispersion of olivine crystal preferred orientation (CPO). Fourier transform infrared spectroscopy analyses show that olivine has very low water contents (1-4 wt. ppm H2O), similar to spinel peridotites from other subduction zones. These low values may record both low water solubility in olivine at low pressure and dehydration during transport and exhumation. Water contents in pyroxenes are highly variable and likely result from spatially heterogeneous melt or fluid percolation. Analysis of olivine CPO indicates dominant activation of both (010)[100] and (001)[100] slip systems, which are characteristic of deformation under high temperature, low stress, low pressure and low to moderate hydrous conditions. Fast S-wave polarization and P- and Rayleigh propagation directions are thus parallel to the mantle flow direction. The pyroxene enrichment by melt-rock reactions is accompanied by dispersion of olivine CPO and induces a significant decrease of the maximum S-wave and P-wave anisotropy in the peridotites. The calculated seismic properties also show that the lowest Vp/Vs ratios (< 1.7) mapped in fore-arc mantle may only be explained by taking in consideration the CPO-induced elastic anisotropy of the peridotites.
ISSN: 0040-1951

hal-00950058
https://hal.archives-ouvertes.fr/hal-00950058
DOI : 10.1016/j.tecto.2013.09.024

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study explores the dynamics of porosity and reactive surface area changes during porous limestone dissolution by CO2-rich water. The Sr and Ca concentrations in both the rock and the outlet solution are used to evaluate the reactive surface area changes of the two rock-forming calcites, i.e. micrite grains and sparite crystals, which have different trace element signatures. The geometric surface area measured with X-ray microtomography decreases slightly whereas the reactive surface area increases continuously with increasing porosity from 20.3 to 30.2%. Surprisingly, changes in reactive surface areas are very different between the two calcites. The reactive surface area changes in the micrite are parabolic while the reactive surface area of sparite increases greatly. The numerical model HYTEC is used to model the change in reactive surface areas during the experiment. Different geometrical models are tested. The model based on spherical-grain dissolution and spherical-pore growth fails to reproduce the experimental results, while the sugar-lump model provides reasonable agreement with the experiment.
ISSN: 0009-2541

hal-00445274
https://hal.archives-ouvertes.fr/hal-00445274
DOI : 10.1016/j.chemgeo.2009.01.032

Éditeur(s) : HAL CCSD Elsevier
Résumé : Differentiation of the Earth's mantle and formation of continental and oceanic crust occur principally through partial melting and extraction of basaltic melt. Among the mantle rocks occurring at the Earth's surface, as tectonically-emplaced massifs, abyssal peridotites or xenoliths, the harzburgites (< 5% clinopyroxene) are widely considered as refractory mantle residues left after extraction of a basaltic component. In contrast, the most fertile lherzolites (15% clinopyroxene) are generally regarded as pristine mantle, only weakly affected by partial melting. In this paper we present new convergent structural and geochemical data from the Lherz massif, the type-locality of lherzolite, indicating that the lherzolites from Lherz do not represent pristine mantle. Detailed structural mapping clearly shows that the lherzolites are secondary rocks formed at the expense of the harzburgites. Variations of major, minor and trace elements through the harzburgite–lherzolite contacts indicate that the lherzolites were formed through a refertilization process involving interaction of refractory, lithospheric mantle with upwelling asthenospheric partial melts. Combined with previously published indications of refertilization in orogenic peridotites, our new observations in Lherz suggest that most lherzolite massifs represent secondary (refertilized) rather than pristine mantle. Together with geochemical data on mantle xenoliths, this indicates that melt transport and melt-rock reaction play a key role on the rejuvenation and erosion of the lithospheric mantle.
ISSN: 0012-821X

hal-00406433
https://hal.archives-ouvertes.fr/hal-00406433
DOI : 10.1016/j.epsl.2007.05.026

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
The mantle above a subducting slab is the site of complex interactions between deformation, partial melting, fluid migration and magma transport. To constrain these interactions and their effects on olivine deformation, we analyze microstructures, crystal preferred orientations, and water contents of peridotite xenoliths entrained by andesites of the Avacha volcano, southern Kamchatka arc. These xenoliths are refractory spinel harzburgites that have coarse-grained microstructures with widely spaced subgrain boundaries and sinuous grain boundaries in olivine, consistent with deformation by dislocation creep under low deviatoric stress (< 13 MPa) and with a significant contribution from diffusional processes. Analysis of crystal preferred orientations (CPO) indicates dominant activation of high-temperature, low-stress {0kl}[100] slip systems in olivine and of(100)[001] in orthopyroxene. In most samples, coarse opx crystals, elongated parallel to the lineation, enclose small olivine grains in crystallographic continuity with neighbouring crystals, indicating crystallization of orthopyroxene at the expense of olivine as a result of reactive percolation of Si-rich fluids coeval with the high-temperature deformation. Secondary crystallization of interstitial orthopyroxene led locally to development of opx-rich lenses parallel to the foliation, characterized by a decrease in olivine grain size and dispersion of the olivine CPO without changing the dominant slip systems. Half of the samples also show acicular orthopyroxene aggregates with which is associated a fine-grained matrix composed of rounded strain-free olivine, orthopyroxene, spinel, and rare amphibole crystals. This matrix occurs pervasively along grain boundaries or forms millimeter-scale irregular lenses and anastomosing veinlets that crosscut the coarse crystals and their ductile deformation structures. Both acicular orthopyroxene and the fine-grained matrix are interpreted as resulting from reactive transport of H2O-rich fluids under static conditions, probably in the lithospheric mantle. Infrared analyses show that olivine contains 1-8 center dot 6 ppm by weight of water. These low water contents are similar to those observed in spinel peridotites from other subduction zones and probably record both the low solubility of water in olivine at low pressure and dehydration during exhumation of the xenoliths. Water contents in orthopyroxene are highly variable (25-506 ppm H2O), probably recording spatially heterogeneous interaction with fluids or melts and compositional disequilibrium in the studied samples. Change in the dominant percolation mechanism from porous flow to fracturing suggests cooling, consistent with the low temperatures estimated from pyroxene thermometry (< 800-900 degrees C). The Avacha xenoliths therefore record pervasive deformation of a region of the mantle under asthenospheric conditions, followed by its accretion to the base of the lithosphere, probably as a result of cooling of the mantle wedge. Percolation of Si-rich fluids or hydrous melts is recorded at all stages; this probably enhanced diffusion and lowered deviatoric stresses during ductile deformation, but did not change the dominant slip direction in olivine from [100] to [001].
ISSN: 0022-3530

hal-00456053
https://hal.archives-ouvertes.fr/hal-00456053
DOI : 10.1093/petrology/egp085

Éditeur(s) : HAL CCSD Elsevier
Résumé : Understanding chemical element mobility during high-pressure metamorphism is paramount to the knowledge of the transformations occurring during the course of eclogite-facies metamorphism. In particular, the role of deformation and fluid circulation appear essential. In order to better decipher this role, we investigated two eclogite-facies samples from the Lindas Nappe in the Bergen arcs (Norwegian Caledonides), which are related to a fluid/deformation metamorphic event. This study, based on detailed microtextural investigations, coupled with major and trace element analyses, either in situ EMPA and LA-ICP-MS or by conventional ICP-MS nebulisation on mineral fractions, illustrates the complexity of chemical reactions accompanying the eclogite- and amphibolite-facies metamorphism. A single eclogite-facies mineral species two eclogite-facies (i.e. phengite and epidote) depicts various chemical features depending on its textural location at thin-section scale. The correlation with the mineralogical reaction occurring in each textural site demonstrates that the compositional variations are inherited from the precursor minerals. Thus, the composition of eclogite-facies minerals is locally controlled by the composition of few hundred-micron domains. On the contrary, alteration phases of the amphibolite facies (symplectite and calcic amphibole) display clear enrichment in LILE, Pb, Sr and LREE compared to their precursor minerals (omphacite and garnet). This supports that the transport of elements at hand-sample scale was enhanced during the retrogression and elements were efficiently delocalised from one textural site to another. The contrasting behaviour of element mobility between peak eclogite-facies metamorphism and retrogression can be explained in terms of rate processes and fluid/deformation activity. During eclogitisation,deformation allows the formation of textural and mineralogical microdomains. Contemporaneously the fluid circulation favours the development of heterogeneities by transport of elements in excess towards areas protected from deformation where phengite-bearing quartz lenses crystallise. This, together with the very fast recrystallisation of eclogite-facies minerals, results in a heterogeneous redistribution of elements at sample scale and in a chemical disequilibrium between different microdomains of hundred-micron size. During retrogression in the amphibolite facies, coeval with long-term ductile deformation, the fluids act as an efficient vector to redistribute the elements from a given textural site to another and, thus, allow to reach, at hand-sample scale, a new chemical equilibrium between the different crystallising phases.
ISSN: 0024-4937

hal-00404602
https://hal.archives-ouvertes.fr/hal-00404602
DOI : 10.1016/j.lithos.2006.10.001

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Numerical programs for simulating flow and reactive transport in porous media is essential for predicting reservoir properties related to CO2 sequestration performance, subsurface storage and risk assessment. In this paper we solve the Navier Stokes' equation using finite difference method, on a simulated porous rock structure, to study the velocity distribution of fluid flowing through it under a constant pressure gradient. A reactive solute carried through the fluid is allowed to interact with the minerals in the rock. This chemical reaction dissolves the mineral which changes the rock structure thus affecting its flow properties. These changes of flow properties are studied with variation in reactive solute concentration and pressure field. The different mechanisms of dissolution responsible for the variation of flow properties for the different parameters is predicted. Before the onset of homogeneous dissolution, variation in porosity follows a power-law behaviour with change in permeability when the latter is scaled by the concentration of the reactive species. The simulation results are compared with available experimental data and found to give a reasonable match.
ISSN: 0022-1694

hal-00757760
https://hal.archives-ouvertes.fr/hal-00757760
DOI : 10.1016/j.jhydrol.2012.05.024

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Before attaining the mantle wedge, where they trigger partial melting, volatiles released from dehydration reactions in the slab have to migrate across a relatively cold (<750 degrees C), peridotite-layer above the incoming slab. In order to unravel the mechanisms allowing for this initial stage of fluid transport, we performed a detailed field and microstructural study of metamorphic prograde peridotites in the Cerro del Almirez ultramafic massif (Betic Cordillera, Spain), where evidences of one of the most important dehydration reactions in subduction zones, the high-pressure antigorite breakdown (P = 1.6-1.9 GPa and T approximate to 680 degrees C), can be mapped in the field. This reaction led to arborescent growth of centimeter-size olivine and orthopyroxene, producing a chlorite-harzburgite with a spinifex-like texture. Microstructural observations and crystal preferred (CPO) mapping show no evidences of solid-state deformation during the prograde growth of olivine and orthopyroxene at the expenses of antigorite. However, a few tens to a hundred meters away from the reaction front, the metamorphic texture is partially obliterated by grain-size reduction in roughly planar conjugate zones, a few mm to meters wide. Grain size reduction zones (GSRZ) are characterized by (1) sharp contacts with undeformed spinifex-like texture domains, (2) important reduction of the olivine grain size (60-250 mu m), (3) olivine color change from brownish to colorless, (4) decrease in the modal amount of orthopyroxene, and (5) at the mm- to cm-scale, irregular shapes and abrupt terminations. Field and microstructural observations exclude that relative displacement took place across these GSRZ. Changes in modal composition imply reactions with fluids undersaturated in silica. Analysis of olivine crystal-preferred orientations (CPO) in GSRZ shows patterns similar, but more dispersed, than those in neighboring spinifex-like domains. It also reveals mm- to cm-scale discrete domains with rather homogeneous crystallographic orientations suggesting inheritance from the preexisting spinifex-like olivines in the host peridotite. Misorientation angles between neighboring grains in the GSRZ show peaks at similar to 5-10 degrees and similar to 20 degrees, but rotations are not crystallographically controlled. Based on these observations, we rule out the formation of the GSRZ by dynamic recrystallization during dislocation creep and propose that they record brittle deformation (microcraking) of the spinifex-like chlorite-harzburgite, probably induced by hydrofracturing at high pressure and relative low temperature conditions (680-710 degrees C). High-pressure hydrofracturing can, thus, be invoked as an efficient mechanism for fluid flow across the cold top-slab mantle layer, hence allowing the slab-derived fluids to ingress in the wedge.
ISSN: 0012-821X

hal-00534035
https://hal.archives-ouvertes.fr/hal-00534035
DOI : 10.1016/j.epsl.2010.06.029

Éditeur(s) : HAL CCSD
Résumé : Differentiation of the lithospheric mantle occurred principally through partial melting and extraction of melts. Harzburgites are generally considered as melting residues whereas lherzolites are regarded as pristine mantle weakly affected by melting. However, some orogenic peridotites show evidence of igneous refertilization. In this context, this work re-investigates the nature of the Lherz lherzolites (Pyrenees), type-locality of lherzolites, described as a piece of preserved fertile mantle. Structural and geochemical data show that these lherzolites are not pristine but formed through a refertilization reaction between MORB-like melts and refractory lithosphere. Moreover, the Lherz peridotites were partly used to infer the composition of the primitive upper mantle and these results may have important implications for the nature of the late veneer. Additionally, crystal-preferred orientations of minerals (CPO) highlight a strong feedback between melt percolation and finite strain in the percolated rocks. CPO variations are ruled by a subtle balance between instantaneous melt fraction and local strain rate. This work also investigated the effect of melt percolation on Hf, Nd and Sr isotopes. Isotope systematics in Lherz shows that strong isotopic decoupling may arise in a percolation front. The modelling suggests that decoupled isotopic signatures are generated during porous flow and governed by the melt/matrix elements concentrations, chemical diffusivities or efficiency of isotopic homogenization. Melt-rock interactions can generate “intraplate-like” isotopic signatures. This suggests that a part of isotopic signatures of mantle-related rocks could be generated by diffusional processes associated with melt transport.
La différenciation du manteau lithosphérique s'est principalement effectuée par fusion partielle et extraction de magmas. Les harzburgites sont généralement considérées comme des résidus de fusion tandis que les lherzolites représentent un manteau originel peu affecté par la fusion. Cependant, certaines péridotites orogéniques montrent des évidences de refertilisation magmatique. Dans ce contexte, ce travail remet en cause la nature primitive des lherzolites de Lherz (Pyrénées), lithotype de la lherzolite. Les données structurales et géochimiques montrent que ces lherzolites ne représentent pas du manteau préservé mais qu'elles se sont formées par une réaction de refertilisation entre un liquide de type MORB et une lithosphère réfractaire. De plus, les orientations préférentielles de réseau (OPR) des minéraux montrent une forte interdépendance entre la percolation magmatique et la déformation finie observée dans les roches percolées. Les variations d'OPR semblent contrôlées par un équilibre subtil entre fraction de liquide instantanée et taux de déformation local. Ce travail a également abordé les effets de la percolation magmatique sur la variabilité isotopique des roches mantelliques. Les résultats montrent qu'un fort découplage isotopique peut s'observer dans un front de percolation. Les modèles suggèrent que le découplage des signatures isotopiques se produit pendant la percolation, gouverné par le rapport des concentrations en éléments (magma/matrice), la diffusivité et le processus d'homogénéisation isotopique. Les réactions magma/roche peuvent générer des signatures isotopiques de type intraplaque. Ceci suggère qu'une part des signatures isotopiques des roches ou laves dérivées du manteau pourrait être produite par des processus diffusionnels associés à du transport de magma.
https://tel.archives-ouvertes.fr/tel-00431325

tel-00431325
https://tel.archives-ouvertes.fr/tel-00431325
https://tel.archives-ouvertes.fr/tel-00431325/document
https://tel.archives-ouvertes.fr/tel-00431325/file/theseleroux08.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We studied the deformation in a partially molten mantle through detailed petrostructural analysis of plagioclase lherzolites from the northwestern part of the central Lanzo massif. These peridotites display a pervasive anastomosed network of millimetre to centimetre-scale plagioclase-rich bands, which grades locally into a planar layering marked by an intercalation of plagioclase-rich and olivine-rich layers up to tens of centimetres wide. Both the anastomosed and the planar layering are subparallel to the deformation fabric, characterized by a foliation defined by the shape-preferred orientation of olivine and by crystal preferred orientation (CPO) of olivine, orthopyroxene, and clinopyroxene. This parallelism, the coexistence of microstructural evidence for melt-rock reactions and for deformation by dislocation creep, and the predominance of axial-[010] olivine CPO patterns, characterized by [010] axes clustered normal to the layering, indicate that deformation and the reactive melt percolation that formed the layering were coeval. Strong heterogeneity in mineral composition in the planar layering domains, with Fe-enrichment in olivine and spinel and highly variable Ti content in spinel in cm-scale plagioclase-rich bands, implies that the latter interacted with higher melt volumes. High Ti contents in pyroxenes and spinel in the anastomosed layering domains point to changes in melt composition, hinting to less effective melt transport. We propose therefore that the planar layering records melt segregation in layers parallel to the shear plane, whereas the anastomosed layering results from melt alignment along grain boundaries subparallel to the shear plane, without segregation. Finite strain in the different layers cannot be quantified, but comparison of the present observations with data from experiments and from other mantle outcrops displaying shear-controlled melt organization suggests that the transition from the anastomosed to the planar layering might record an increase in finite strain, that is, strain localization associated with variations in the instantaneous melt fraction.
ISSN: 0040-1951

hal-01053509
https://hal.archives-ouvertes.fr/hal-01053509
DOI : 10.1016/j.tecto.2014.01.007

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Underground CO2 sequestration is highly recommended as an effective means of significantly decreasing CO2 concentration in the atmosphere. Mineral storage is the more secure technology, but requires the presence of high concentration of divalent cations in the pore-fluid. Results from CO2 percolation experiments through chlorite/zeolite-rich sandstone samples from the Pretty Hill Formation (Otway Basin, Australia) are presented. The dissolution of the laumontite (7 wt.%) and chamosite (7 wt.%) are the potential sources of calcium, iron and magnesium required for carbonate precipitation. The percolation experiment was setup to reproduce, at laboratory scale, the in situ temperature and pressure conditions (T = 95 degrees C and P = 10 MPa). The fluid injected at constant flow rate is a rock-equilibrated brine subsequently enriched in CO2 up to partial pressure of 6 MPa. We observe feldspars, laumontite and chamosite dissolution, kaolinite and silica precipitation and a noticeable sink of CO2 in the sample which is attributed to the precipitation of both amorphous carbon due to the reduction of CO2 and Fe-rich carbonate. Permeability decreases of about one order of magnitude due to the localization of the kaolinite precipitation in the main flow paths, while porosity increases. The high reactivity of this sandstone makes this reservoir a valuable target for CO2 mineralization, but the associated permeability decrease may limit the injection rate and the spreading of the CO2 in the reservoir.
ISSN: 0009-2541

hal-00712829
https://hal.archives-ouvertes.fr/hal-00712829
DOI : 10.1016/j.chemgeo.2011.11.018

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Most peridotite massifs and mantle xenoliths show a wide range of isotopic variations, often involving significant decoupling between Hf, Nd and Sr isotopes. These variations are generally ascribed either to mingling of individual components of contrasted isotopic compositions or to time integration of parent-element enrichment by percolating melts/fluids, superimposed onto previous depletion event(s). However, strong isotopic decoupling may also arise during porous flow as a result of daughter-elements fractionation during solid-liquid interaction. Although porous flow is recognized as an important process in mantle rocks, its effects on mantle isotopic variability have been barely investigated so far. The peridotites of the Lherz massif (French Pyrenees) display a frozen melt percolation front separating highly refractory harzburgites from refertilized lherzolites. Isotopic signatures observed at the melt percolation front show a strong decoupling of Hf from Nd and Sr isotopes that cannot be accounted for by simple mixing involving the harzburgite protolith and the percolating melt. Using one dimensional percolation-diffusion and percolation-reaction modeling, we show that these signatures represent transient isotopic compositions generated by porous flow. These signatures are governed by a few critical parameters such as daughter element concentrations in melt and peridotite, element diffusivity, and efficiency of isotopic homogenization rather than by the chromatographic effect of melt transport and the refertilization reaction. Subtle variations in these parameters may generate significant inter-isotopic decoupling and wide isotopic variations in mantle rocks. (C) 2009 Elsevier B.V. All rights reserved.
ISSN: 0012-821X

hal-00413135
https://hal.archives-ouvertes.fr/hal-00413135
DOI : 10.1016/j.epsl.2008.12.033

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
Carbonation of ultramafic rocks in geological reservoirs is, in theory, the most efficient way to trap CO2 irreversibly; however, possible feedback effects between carbonation reactions and changes in the reservoir permeability must be considered to realistically assess the efficiency and sustainability of this process. We investigated changes in the hydrodynamic properties of sintered dunite samples by means of percolation experiments, under conditions analogous to that of in situ carbonation. Our results show that carbonation efficiency is controlled by the local renewal of the reactants and the heterogeneity of the pore structure. Preferential flow zones are characterized by the formation of magnetite and of a silica-rich layer at the olivine surfaces, which eventually inhibits olivine dissolution. Conversely, sustainable olivine dissolution together with coprecipitation of magnesite, siderite, and minor Mg-TOT-phyllosilicates, occur in reduced-flow zones. Thus carbonate precipitation only decreases porosity in zones where diffusion-controlled transport is dominant. Consequently, while high flow rates will decrease the carbonation efficiency of the reservoir and low flow rates may reduce the permeability irreversibly close to the injection point, moderate injection rates will ensure a partial carbonation of the rock and maintain the reservoir permeability.
ISSN: 0013-936X

hal-00424540
https://hal.archives-ouvertes.fr/hal-00424540
DOI : 10.1021/es8018429

Éditeur(s) : HAL CCSD
Résumé : In order to minimize CO2 atmospheric concentration, a solution consists in sequestrating CO2 in geological reservoirs. To estimate long term risks, it is necessary to quantify the couplings between reaction processes as well as structural and hydrodynamical modifications. We realised two experimental benches enabling injecting CO2-enriched-brine in conditions corresponding to in situ storage (T < 200 oC and P < 200 bar) and developed
an experimental protocol using X-Ray microtomography and fluid and rock analyses in order to measure the variations of physical and chemical parameters.
The study of carbonated reservoirs near the injection well, allows quantifying different k-phi relationships depending on the dissolution processes and triggered by the local fluid chemical composition and initials conditions. Away from the injection well, we observe carbonate precipitation decreasing the permeability. The study of fracturated caprock samples shows that alternative percolation of CO2-enriched-brine and CO2 gas increases the fracture permeability.
The study of silicated rocks indicates carbonate precipitation in zeolite sandstone and sintered dunite grains. Nevertheless, in zeolite sandstone we also observe the precipitation of clay particles located in the uid pathways which decrease strongly the permeability.
Afin de minimiser la concentration en CO2 dans l'atmosphère une solution consiste à le séquestrer dans les réservoirs géologiques. Pour évaluer les risques à long terme, il est nécessaire de quantifier les couplages entre les processus réactionnels et les modifications structurales et hydrodynamiques. Dans cette optique, nous avons construit deux dispositifs expérimentaux permettant d'injecter des saumures chargées en CO2 dans les conditions de stockage (T < 200 °C et P < 200 bar) et mis en oeuvre un protocole expérimental utilisant la microtomographie RX et l'analyse des roches et des fuides pour quantifier les variations des paramètres physiques et chimiques. Dans le cas des réservoirs carbonatés, on observe, près du puits d'injection, une forte variabilité des relations k-phi en fonction du régime de dissolution contrôlé par la chimie locale du fluide, ainsi que par les conditions initiales. A plus grande distance, on observe des processus de précipitation diminuant fortement la perméabilité. L'étude des roches de couverture fracturées (argilite) a montré qu'une percolation alternée d'une saumure chargée en CO2 et de CO2 gaz augmentait la perméabilité de fracture. Dans le cas des roches silicatées, la précipitation de carbonates est mise en évidence aussi bien dans les grès à zéolites que dans les frittés de dunite de San Carlos. Cependant, dans les grès à zéolites, la précipitation d'une phase argileuse est observée dans les chemins d'écoulement et engendre une forte diminution de la perméabilité.
https://tel.archives-ouvertes.fr/tel-00416408

tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408/document
https://tel.archives-ouvertes.fr/tel-00416408/file/These_Luquot.pdf

Éditeur(s) : HAL CCSD Wiley-Blackwell
Résumé : International audience
The Lanzo peridotite massif is a fragment of oceanic lithosphere generated in an ocean-continent transition context and eclogitized during alpine collision. Despite the subduction history, the massif has preserved its sedimentary oceanic cover, suggesting that it may have preserved its oceanic structure. It is an exceptional case for studying the evolution of a fragment of the lithosphere from its oceanization to its subduction and then exhumation. We present a field and petrological study retracing the different serpentinization episodes and their impact on the massif structure. The Lanzo massif is composed of slightly serpentinized peridotites (<20% serpentinization) surrounded by an envelope of foliated serpentinites (100% serpentinization) bordered by oceanic metabasalts and metasedimentary rocks. The limit between peridotites and serpentinites defines the front of serpentinization. This limit is sharp: it is marked by the presence of massive serpentinites (80% serpentinization) and, locally, by dykes of metagabbros and mylonitic gabbros. The deformation of these gabbros is contemporaneous with the emplacement of the magma. The presence of early lizardite in the peridotites testifies that serpentinization began during the oceanization, which is confirmed by the presence of meta-ophicarbonates bordering the foliated serpentinite envelope. Two additional generations of serpentine occur in the ultramafic rocks. The first is a prograde antigorite that partially replaced the lizardite and the relict primary minerals of the peridotite during subduction, indicating that serpentinization is an active process at the ridge and in the subduction zone. Locally, this episode is followed by the deserpentinization of antigorite at peak P-T (estimated in eclogitized metagabbros at 2-2.5 GPa and 550-620 °C): it is marked by the crystallization of secondary olivine associated with chlorite and/or antigorite and of clinopyroxene, amphibole and chlorite assemblages. A second antigorite formed during exhumation partially to completely obliterating previous textures in the massive and foliated serpentinites. Serpentinites are an important component of the oceanic lithosphere generated in slow to ultraslow spreading settings, and in these settings, there is a serpentinization gradient with depth in the upper mantle. The seismic Moho limit could correspond to a serpentinization front affecting the mantle. This partially serpentinized zone constitutes a less competent level where, during subduction and exhumation, deformation and fluid circulation are localized. In this zone, the reaction kinetics are increased and the later steps of serpentinization obliterate the evidence of this progressive zone of serpentinization. In the Lanzo massif, this zone fully recrystallized into serpentinite during alpine subduction and collision. Thus, the serpentinite envelope represents the oceanic crust as defined by geophysicists, and the sharp front of serpentinization corresponds to an eclogitized seismic palaeo-Moho.
ISSN: 0263-4929

hal-00823051
https://hal.archives-ouvertes.fr/hal-00823051
DOI : 10.1111/jmg.12008