Éditeur(s) : HAL CCSD
Résumé : The main purpose of this thesis was to characterize and to model the hydrodynamic and thermochemical processes leading to the alteration of the wellbore cement materials under borehole conditions. Percolation experiments were performed on fractured cement samples under CO2 storage conditions (60°C and 10MPa). Injection flow rate was dictated by the fracture aperture of each sample. CO2 enriched brine was flowed along the fracture aperture, and permeability changes as well as chemical evolution of major cations were continuously acquired during the experiment time. Reaction paths developed by the alteration of the cement were characterized using microtomography and ESEM images. The experiments conducted using samples presenting large fracture apertures during 5h showed that permeability was maintained constant during the experiment time. Three reacted layers were displaying by the alteration of portlandite and CSH. Long term experiment (26h) conducted with large initial fracture aperture showed a decrease of the permeability after 15hours of CO2 exposure. Otherwise, experiments performed on samples presenting narrow apertures indicated the conversion of portlandite and CSH to calcite leading to the permeability reduction and the fracture clogging. Assemblages of phases and chemical changes were modelled using GEMS-PSI speciation code. We studied also using a coupled transport-reactive model the conditions leading to the cement alteration and the formation of associated layers.
L'objectif de cette thèse était de modéliser à partir des expériences de percolation-réactive, les processus hydrodynamique et réactionnel qui gouvernent l'altération des ciments de puits. Différentes expériences ont été réalisées dans des conditions représentatives de celles du stockage du CO2. Des échantillons fracturés ont été utilisés pour injecter une saumure enrichie en CO2 à 60°C et 10MPa et à différentes pressions partielles de CO2. Le débitd'injection variait en fonction des propriétés hydrauliques de l'échantillon exposé. L'injection d'une saumure enrichie en CO2 à débit constant à travers une fracture supposée plane a permis d'étudier les modifications des propriétés hydrodynamiques et ces conséquences sur la géochimie et la microstructure du ciment altéré. L'impact dynamique de l'évolution microstructurale a été mis en évidence. Les expériences conduites sur des échantillons présentant de larges ouvertures, réalisées sur une durée de 5 h, ont montré que la perméabilité était maintenue constante le long de l'expérience. Trois couches d'altération se sont développées consécutivement à la dissolution de la portlandite et la décalcification des CSH. L'altération a entrainé la précipitation des carbonates et de la silice amorphe à proximité de la fracture. Dans le cas d'une expérience longue durée appliquant les mêmes conditions que précédemment on a observé que la croissance de la silice amorphe a entrainé la diminution de la perméabilité. Par ailleurs les expériences effectuées sur des échantillons présentant de faibles ouvertures, ont indiqué que la conversion de la portlandite en calcite conduit au colmatage de la fracture. L'évolution des assemblages de phases conduisant à la formation des carbonates et de la silice amorphe a été modélisée à partir du code géochimique GEMS. Les mécanismes de diffusion et les processus de mise en place des couches d'altération ont été étudiés à partir d'un modèle analytique et d'un modèle de transport réactif à partir du code géochimique PHREEQC.
https://tel.archives-ouvertes.fr/tel-01038034

tel-01038034
https://tel.archives-ouvertes.fr/tel-01038034
https://tel.archives-ouvertes.fr/tel-01038034/document
https://tel.archives-ouvertes.fr/tel-01038034/file/theseabdoulghafour.pdf

Éditeur(s) : Elsevier Science Bv
Résumé : Although Ni isotopes have been shown to be significantly fractionated in terrestrial samples, their use in continental environmental studies has not yet been evaluated. The present study focuses on an ultramafic (UM) massif (Barro Alto, Goias, Brazil) because such areas are naturally rich in Ni. We present developed lateritic weathering profiles. The goal of the study is to evaluate the potential of using Ni isotopes in environmental continental studies by combining its isotopic signature with mineralogy, in order to better understand the geochemical cycling of Ni in UM settings during weathering. As such, Ni isotope values were measured in samples from the Barro Alto UM complex in the main stages of the lateritic weathering profile of UM rocks, including bedrock, ores (saprolitic and lateritic samples) and soil. The mineralogical composition of the samples, with a focus on the different Ni-bearing minerals, was also determined to decipher the potential links between isotopic fractionation and weathering dynamics. Isotopic signatures (δ60Ni) from the natural Ni geochemical cycle include: bedrock samples (δ60Ni = 0.28 ± 0.08‰), ore samples (saprolitic and lateritic, δ60Ni from -0.60 to 0.30‰) and soil samples (δ60Ni from -0.19 to -0.02‰). An overall trend of heavier isotope depletion was observed in the solid phase during weathering (Δ60NiSoil-Bedrock = -0.47‰). The mineralogical results were consistent with the literature and showed that the mineralogy of the lateritic part and soil was dominated by Fe-oxides, whereas clay minerals were the primary Ni phase scavengers in the saprolitic part of the profile. Thus, the formation of Ni-bearing clay minerals and Fe-oxides appeared to lead to depletion in heavier isotopes, which indicates preferential export of heavy isotopes in the dissolved phase. This result is consistent with isotopic signatures measured in the exchangeable pool of the solid phase (Δ60Niexch-total up to 0.47‰), and Ni isotopes appear to be a promising tracer to better understand the biogeochemical Ni cycling on the Earth’s surface.
Chemical Geology (0009-2541) (Elsevier Science Bv), 2015-05 , Vol. 402 , P. 68-76

Droits : 2015 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/00254/36553/35098.pdf
DOI:10.1016/j.chemgeo.2015.02.039
http://archimer.ifremer.fr/doc/00254/36553/

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
Solidus melting phase relations are reported for carbonated eclogite in the system CaO-MgO-Al2O3-SiO2-CO2 at 12 to 25 GPa. From 12 to 16 GPa, melts are in equilibrium with clinopyroxene, stishovite, garnet, aragonite, and magnesite. At 20 and 25 GPa, melts are in equilibrium with garnet, stishovite, calcium-alumino silicate, calcium perovskite, and magnesite. Melting reactions demonstrate that from 12 to 16 GPa, stishovite is in reaction with the melt. At 20 and 25 GPa, garnet and stishovite together are produced upon melting of model, carbonated eclogite. At 20 and 25 GPa, calcium perovskite is also the phase that contributes the most toward liquid production. Melt compositions at all pressures are carbonatitic, with roughly 37-40 wt% dissolved CO2. From 12 to 16 GPa, the liquids are calciocarbonatites with Ca#(molar) of similar to 69-71; liquid compositions become less calcic with Ca# of similar to 52-55 at 20 and 25 GPa. Given these melting phase relations, suitable subduction zone adiabats do not intersect the solidus of model carbonated eclogite at depths investigated in the present study. Hence, on this basis, it is fair to say that carbonated eclogite possibly avoids melting in subduction zone settings, thereby delivering carbonate to at least moderate depths in the Earth. However, owing to local heating events, small-degree melting of carbonated eclogite is not completely precluded, and the liquids liberated from this melting can be viewed as agents of chemical mass transfer in the deep Earth. At present, however, geochemical consequences of subduction-related melting of carbonated eclogite are difficult to evaluate.
ISSN: 0148-0227

hal-00566560
https://hal.archives-ouvertes.fr/hal-00566560
DOI : 10.1029/2009JB006457