Éditeur(s) : HAL CCSD
Résumé : East African Rift (EAR) is the divergent plate boundary. EAR exposes different stages of extension, from early stage rifting in Tanzania to oceanic accretion in Afar (Ethiopia). Manyara basin is the southernmost rift system of the east branch of EAR with recent volcanism (< 1.5 Ma) and a seismic swarm in the lower crust (20 – 40 km). Due to its location and tectonic setting, the Manyara basin offers the opportunity to study the earliest stage of rift initiation. Manyara volcanism is composed of several types of hyper-alkaline lavas as Mg-nephelinites (Mg# > 55) (Labait, Kwaraha), calciocarbonatite (Kwaraha) and evolved nephelinites (Mg# < 35) (Hanang).Mg-nephelinites (Labait and Kwaraha) are primary lavas mainly composed of olivine and clinopyroxene (cpx). Geochemical modelling from trace elements suggests that these primary magmas result from a degree of partial melting < 1 % from a CO2-garnet-phlogopite-bearing peridotite. These magmas have an asthenospheric source at depth > 120 km (lava carries xenoliths with equilibrium conditions > 4 GPa). The minerals were crystallized from a magma with a low H2O content (0.1 and 0.5 wt% H2O). The calciocarbonatite and evolved nephelinites are derived from Mg-nephelinites by fractional crystallization and immiscibility processes. Hanang nephelinites are silica- and alkaline-rich lavas (44.2 – 46.7 wt % SiO2, 9.5 –12.1 wt % Na2O+K2O, respectively) composed by cpx, Ti-garnet, nepheline, apatite and titanite. Complex zonation of cpx (e.g. abrupt change of Mg#, Nb/Ta, and H2O) and trace element patterns of nephelinites record magmatic differentiation involving open system with carbonate-silicate immiscibility and primary melt replenishment. The low H2O content of cpx (3 – 25 ppm wt. H2O) indicates that at least 0.3 wt % H2O was present at depth during carbonate-rich nephelinite crystallization at 340 – 640 MPa and 1050 – 1100 °C. The study of hosted-nepheline melt inclusions from Hanang allows constraining the late magmatic evolution of nephelinites during storage and magma ascent. Melt inclusions are composed by a silicate trachytic glass, a carbonate phase and a shrinkage bubble. Trachytic glass contains high content in CO2 (0.43 wt %, SIMS analyses), sulfur (0.21 – 0.92 wt % S), chlorine (0.28 –0.84 wt % Cl) and H2O low content (< 0.1 wt %, Raman analyses). Immiscibility process leading to the formation of carbonate occurs in a closed system during rapid magma ascent between 200 – 500 MPa. The carbonate phase is a Ca-Na-K-S-rich and anhydrous carbonate (33 wt % CaO, 20 wt % Na2O, 3 wt % K2O, and 3 wt % S). The pre-immiscible liquid has a phonolitic composition with 6 ± 1.5 wt % CO2 at 700 MPa. A preliminary study of melt inclusions by XANES spectroscopy and whole rocks by Mössbauer spectroscopy was used to determine these Manyara lavas were formed at oxidizing conditions (~ ΔFMQ +1.5).The early stage rifting volcanism (Manyara Basin) is characterized by CO2-rich and H2O-poor magmas from at least 120 km below the rift escarpment. The presence of CO2-rich magmas and the small amount of volcanic rocks erupted at the surface may indicate that the storage and percolation of these magmas at depth is a potential trigger for deep seismic swarms.
Le rift Est africain (REA) est une frontière de plaque en extension. Ce rift présente plusieurs stades d’extension, de l’initiation du rift en Tanzanie jusqu’à l’accrétion océanique en Afar. Le bassin de Manyara se situe le plus au sud de branche Est du REA. Il est caractérisé par la présence de volcanisme récent (< 1,5 Ma) et d’un essaim sismique dans la croûte inférieure (20 – 40 km). De par sa localisation et son contexte tectonique, le bassin de Manyara offre l’opportunité d’étudier le stade le plus précoce de l’initiation du rift. Le bassin de Manyara est composé de plusieurs types de laves hyperalcalines, les néphélinites magnésiennes (Mg# > 55) (Labait, Kwaraha), de calciocarbonatite (Kwaraha) et des néphélinites différenciées (Mg# < 35) (Hanang).Les néphélinites magnésiennes (Labait et Kwaraha) sont des laves primaires composées d’olivines et de clinopyroxènes (cpx). La modélisation géochimique des éléments en trace suggère que ces magmas primaires résultent d'un degré de fusion partielle ≤ 1 % à partir d'une péridotite à grenat et phlogopite. Ces magmas proviennent d’une profondeur > 120 km (présence de xénolites avec des conditions d’équilibre > 4 GPa). Les minéraux ont cristallisés à partir d’un magma pauvre en eau (0,1 et 0,5 pds % H2O). La calciocarbonatite et les néphélinites différenciés sont issues des néphélinites magnésiennes par cristallisation fractionnée et processus d’immiscibilité. Les néphélinites du Hanang sont riches en éléments alcalins (9,5 – 12,1 pds % Na2O+K2O) et en silice (44,2 – 46,7 pds% SiO2) et sont composés de cpx, grenat, néphéline, titanite et apatite. La zonation complexe dans les cpx (par exemple, changement brusque de Mg#, Nb/Ta, et H2O) implique une différenciation magmatique en système ouvert avec immiscibilité de liquide carbonaté et silicaté ainsi qu’un remplissage de la chambre magmatique avec des liquides primaires. La faible teneur en eau des cpx (3 – 25 ppm H2O) indique la présence d’un magma pauvre en eau (0,3 pds % H2O) lors de la cristallisation des cpx à des conditions crustales (340 – 640 MPa et 1050 – 1100 °C). L’étude des inclusions vitreuses dans les néphélines de Hanang permet de contraindre l'évolution magmatique tardive des néphélinites et le comportement des éléments volatils (CO2, H2O, S, F, Cl) lors du stockage et de la remontée du magma. Les inclusions vitreuses sont composées d’un verre trachytique, d’une phase carbonatée et d’une bulle de rétraction. Le verre trachytique contient du CO2 (0,43 pds % CO2, analyses SIMS), du soufre (0,21 à 0,92 pds% S), du chlore (0,28 – 0,84 pds % Cl) et très peu d’H2O (< 0,1 pds % H2O, analyses Raman). Le processus d’immiscibilité conduisant à la formation du carbonate se produit dans un système fermé pendant l'ascension rapide du magma, entre 200 – 500 MPa. La phase carbonatée est un carbonate anhydre et riche en Ca-Na-K-S (33 pds % CaO, 20 pds % Na2O, 3 pds % K2O, et 3 pds % S). Le liquide pré-immiscible a une composition phonolitique avec 6 ± 1,5 pds % CO2 à une pression de 700 MPa. Une étude préliminaire des inclusions par spectroscopie XANES et des roches par spectroscopie Mössbauer a permis de déterminer que les laves de Manyara se sont formées à conditions oxydantes (~ ∆FMQ +1,5).À l’initiation du rift, le volcanisme dans le bassin de Manyara est caractérisé par des magmas riches en CO2 et pauvres en H2O issus d’au moins 120 km de profondeur sous l'escarpement du rift. La présence de ces magmas riches en CO2 et la faible quantité de roches volcaniques émises à la surface peuvent indiquer que le piégeage et la percolation de ces magmas en profondeur est un déclencheur potentiel des essaims sismiques profonds.
https://tel.archives-ouvertes.fr/tel-01563231

NNT : 2016MONTT114
tel-01563231
https://tel.archives-ouvertes.fr/tel-01563231
https://tel.archives-ouvertes.fr/tel-01563231v2/document
https://tel.archives-ouvertes.fr/tel-01563231/file/2016_BAUDOUIN_archivage.pdf

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
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 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
A shallow field experimental site for CO2 injection was established at Maguelone (Languedoc, France), in order to test in an integrated manner a suite of surface and downhole hydrogeophysical monitoring methods. The objective is to improve monitoring of gas transport in the shallow subsurface and to determine the sensitivity of CO2 monitoring systems for leakage detection. The site offers a natural laboratory to study the processes associated with CO2 injection in a clastic and clay-rich context saturated with saline fluids. Prior to CO2 injection, three nitrogen (N2) injections were undertaken in 2012 to measure the site response to neutral gas injection. In 2013, a volume of 111 m3 (mass of 220 kg) of CO2 was injected during 3.5 h at 15 m depth. During each experiment, the gas plumes were successfully detected from pressure monitoring, time-lapse induction logging and downhole resistivity monitoring with dipole–dipole array. Increases in resistivity are attributed to free gas propagation (either N2 or CO2) whereas decreases in resistivity correlate with CO2 dissolution in the pore fluid. Chemical analyses confirm this hypothesis with a decrease in pH and an increase in the concentration of dissolved species in the latter case.
ISSN: 1750-5836

hal-01355943
https://hal.archives-ouvertes.fr/hal-01355943
DOI : 10.1016/j.ijggc.2015.12.005

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
In situ mineralization of CO2 in ultramafic rock-hosted aquifers is one of the promising solutions for decreasing CO2 concentrations in the atmosphere. Naturally altered ultramafic rocks suggest that carbonation processes are controlled by local heterogeneities in the structure of the rock and fluid transport at the water-rock interfaces. We studied the role of rock crystallographic anisotropy relative to the global fluid flow direction on the mineralization of CO2 by means of electron microscope analyses from the macro- to the micrometer scale (EBSD-FIB). The sample used for the measurements was a hot pressed olivine core percolated by water enriched in CO2 (pCO2 = 10 MPa) at 180 °C. During the percolation experiment, olivine was dissolved and two types of carbonates, dolomite, and magnesite, were precipitated on olivine surfaces. The results showed that the dissolution of olivine is controlled by its crystallographic properties as shown by the development of etch-pits only on the (010)ol planes and with elongated shapes parallel to the [010]ol axes. In contrast, the precipitation of carbonates is governed by hydrodynamic properties. Carbonates are heterogeneously distributed in the percolated rock. They are mainly located along the moderate (for dolomite) and the minor (for magnesite) flow paths, both oriented parallel to the principal fluid flow direction, which allow carbonates to be supplied with divalent cations (e.g., Ca2+, Mg2+, and Fe2+). In these flow paths, carbonate growth is systematically oriented normal to the flow that facilitates the development of chemical gradients with cationic supersaturation conditions for carbonate precipitation near the walls.In natural systems, the (010)ol planes are parallel to the Moho and the (100)ol planes are vertical; our study suggests that flow of CO2-rich fluids will induce precipitation of carbonates localized along, and preferentially clogging, vertical flow paths while favoring olivine dissolution along horizontal fluid pathways. This dual control of structure and fluid flow on carbonation mechanisms could be an important parameter allowing sustainable CO2 storage in peridotites, while limiting the risks of leakage toward the surface.
ISSN: 0003-004X

hal-01143393
https://hal.archives-ouvertes.fr/hal-01143393
DOI : 10.2138/am-2015-4913

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We describe an experimental system including monitoring of temperature, pressure, pH, oxidation reduction potential and optical density at 600 nm, designed for studying the role of microorganisms on the geological sequestration Of CO2 and its transformation into solid carbonate phases. Measurements were performed in an artificial ground water (AGW) supplemented with urea (2 g.l(-1)) and equilibrated at controlled temperatures with a gaseous phase before bacterial inoculation. We used the ureolytic strain Bacillus pasteurii as a model carbonate precipitating bacteria and showed that it can successfully promote strong pH increases by ureolysis in the AGW equilibrated with CO2 pressures of up to I bar. Increasing salinities (5.8,13.5 and 35.0 g.l(-1)) have a positive effect on the rate of pH increase, whereas the effect of increasing temperatures (30,35 and 38 degrees C) is less important. Calcium is also shown to have a specific positive influence on the rate of ureolysis. The number of viable cells present in solution decreases greatly during the carbonate precipitation event but the population partially recovers once precipitation is over.
ISSN: 0009-2541

hal-00445282
https://hal.archives-ouvertes.fr/hal-00445282
DOI : 10.1016/j.chemgeo.2008.12.012

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
Claystone caprocks are often the ultimate seal for CO2 underground storage when residual CO2 gas reaches the reservoir top due to buoyancy. Permeability changes of a fractured claystone due to seepage of CO2-enriched brine and water vapor-saturated CO2 gas are investigated. Results show that brine flow induces a large porosity increase (up to 50%) in the vicinity of the fracture due to dissolution of calcite and quartz, while permeability remains unchanged. Conversely, cyclic flows of CO2-brine and CO2-gas increase the fracture aperture abruptly after each gas flow period, producing a progressive decrease of the caprock seal capacity. Aperture increase is controlled by decohesion of the clay framework within a micrometer-scale-thick layer induced by CO2-gas acidification. Results show that hydraulic aperture increases linearly with duration of the preceding CO2-brine flow period, emphasizing the kinetic control of the quartz grains dissolution during the brine flow periods.
ISSN: 0094-8276

hal-00412332
https://hal.archives-ouvertes.fr/hal-00412332
DOI : 10.1029/2008GL034467

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Saline aquifers in deep sedimentary formations are considered the primary candidates for geological storage of CO2, due to their large volumetric capacity that would be sufficient to meet the needs for CCS storage space in a global scale. In comparison to depleted oil and gas reservoirs the deep saline aquifers are, however, less investigated as there has previously been little economic interest in them. Effective methods for characterizing the storage aquifers are crucial for a successful implementation of any CCS project and therefore being developed and transferred from other applications in a various CCS projects.The objective of EU FP7 funded project MUSTANG project (A multiple space and time scale approach for the quantification of deep saline formations for CO2 storage, www.co2mustang.eu) has been to develop methods for characterizing saline aquifers and for understanding their properties. An essential part of this was establishment of a CO2 injection site at Heletz, Israel, where small-scale scientifically motivated injection experiments are planned to be carried out in presently ongoing continuation projects TRUST (http://trust-co2.org/) and CO2QUEST (www.co2quest.eu).While a large number of publications has been already produced based on the work in the MUSTANG project and its successors, and published in different journals, including this one, the objective of this Special Edition has been to gather some of the concluding work in the same journal issue. The focus has in particular been in summarizing the site characterization work carried out at the Heletz site, thereby providing readers an easy overview of the findings and characteristics of the site. In addition, some related work from some of the other sites investigated in MUSTANG project is also included, namely work from the sites Hontomin, Maguelone and a natural analog site in the North Sea. The results are intended to add to our understanding on relevant properties of geological formations as candidates for CO2 geological storage.
ISSN: 1750-5836

hal-01356326
https://hal.archives-ouvertes.fr/hal-01356326
DOI : 10.1016/j.ijggc.2016.02.007

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The main goal of the monitoring stage of Carbon Capture and Storage (CCS) is to obtain an accurate estimation of the subsurface CO2 accumulation and to detect any possible leakage. Laboratory experiments are necessary to investigate the small scale processes governing the CO2–brine–rock interaction. They also provide a means to calibrate the results coming from field scale geophysical methods. In this work we set up an experimental system which is able to perform Electrical Resistivity Tomography (ERT) measurements on centimeter-scale rock samples at various P–T conditions. We present the results of two new experiments related to CO2 monitoring, performed on a cylindrical (4 × 8 cm) Fontainebleau rock sample. In the first one, we have quantified the CO2 saturation at different volume fractions, representing zones from a deep saline aquifer with varying degrees of saturation. In the second one, we have monitored and quantified the effect of CO2 dissolution in the brine at a pressure of 40 bar during eight days, emulating the invasion of CO2 into a shallow aquifer. Results highlight the importance of accounting for the contribution of surface conductivity in highly CO2-saturated regions, even in clay-free rocks, and also for brine conductivity variation due to CO2 dissolution. Ignoring any of these effects will end up in a CO2 saturation underestimation. We present a modified CO2 saturation equation to account for these two influences.
ISSN: 0926-9851

hal-01356323
https://hal.archives-ouvertes.fr/hal-01356323
DOI : 10.1016/j.jappgeo.2016.03.039

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
GenMol (TM) code is used to simulate Atomic Force Microscopy (AFM) tests at a kaolinite/brine/kaolinite contact, the confined fluid in sub-nanometre interspaces being in equilibrium with an external multi-species solution. The attraction/repulsion effort, i.e. the derivative versus the interspace aperture h of the interaction energy between both kaolinite faces, is computed versus the variable composition of the confined fluid (see for the method Part I of this work). Two external solutions are tested. Solution Si is a neutral brine (pH=7.5) leading to a possible attraction for apertures lower than 7 angstrom. Solution S2 is an acidified brine (pH=3.2) leading to repulsion whatever may be the aperture h. These two AFM simulations prove the existence of a critical pH value (3.2 < pH(crit) < 7.5) of the external solution, below which the acidification of a natural brine in a CO2 confinement inhibits adhesion between kaolinite aggregates.
ISSN: 0022-0248

hal-00544678
https://hal.archives-ouvertes.fr/hal-00544678
DOI : 10.1016/j.jcrysgro.2010.08.012

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
To test the impact of fluid flow on the reactivity of porous (ultra-)mafic rocks, reactive percolation experiments were realized during which CO2-enriched water was injected at two different injection rates (Q = 0.1 and 1 mL h−1) through sintered analogues of olivine-accumulation zones in basaltic flows at temperature and fluid composition conditions (T = 180 °C; NaHCO3 buffered solution) favorable for CO2-mineralization (carbonation).All experiments resulted in silicate dissolution, carbonate precipitation upstream and (proto-)serpentine formation downstream indicating a decrease in the fluid reactivity along flow paths. The measured bulk carbonation rates ranged from 4 to 7 × 10−8 s−1; these values were significantly lower than previously published values of olivine carbonation rate obtained on powders in closed batch and flow-through reactors. Our study show complex couplings, at pore scale, between fluid flow, localization of reaction zones, and chemical reaction kinetics which in turn control hydrodynamic properties, carbonation rate and efficiency and fluid reactivity. This results in carbonation rates being higher when injection rates are high and permeability ultimately controlling carbonation reactions by limiting fluid input. During experiments, notable changes in permeability occurred for only minor changes in porosity indicating a control by the geometry of the porous network: heterogeneities in the distribution of flow paths favored the localization of precipitated minerals which in turn resulted in the closure of flow paths. This mechanism was particularly efficient at low injection rates. These results imply that controlling the injection rate could allow enhancing/limiting the efficiency of in situ carbonation.
ISSN: 0883-2927

hal-01115284
https://hal.archives-ouvertes.fr/hal-01115284
DOI : 10.1016/j.apgeochem.2014.11.024

Éditeur(s) : HAL CCSD Wiley
Résumé : International audience
The paper is motivated by the long term safety analysis of the CO 2 geological storage. We present a methodology for the assessment of the ge-omechanical impact of progressive rock dissolution. The method is based on the use of X-ray tomography and the numerical dissolution technique. The influence of evolution of the microstructure on the macroscopic properties of the rock is analysed by using periodic homogenization method. The numerical computations show progressive degradation of all components of the stiffness (orthotropic) tensor. Moreover, the evolution of associated mass transfer properties (as tortuosity and conductivity tensors), by using the periodic homogenization method, is also calculated. The correlation between the mechanical parameters and the transfer properties during the dissolution pro-cess is presented. The results show that the highest increase of the hydraulic conductivity (in direction Y) is not associated with the highest decrease of Young modulus in this direction. Moreover, the highest decrease of Young modulus (in the direction X) is not associated with percolation in this direction. Finally, an incremental law to calculate settlement, in case of a rock with evolving microstructure, is proposed. The solution of the macroscopic settlement problem under constant stress and drained conditions showed that the geomechanical effects of the rock dissolution are rather limited.
ISSN: 0363-9061

hal-01104204
https://hal.archives-ouvertes.fr/hal-01104204
https://hal.archives-ouvertes.fr/hal-01104204/document
https://hal.archives-ouvertes.fr/hal-01104204/file/Numerical_computations_rock_dissolution_Wojtacki_al_2014.pdf
DOI : 10.1002/nag.2316

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) : HAL CCSD American Geophysical Union
Résumé : International audience
A CO2-rich brine core-flood experiment in calcite limestone for conditions representative of underground storage (P = 12 MPa and T = 100°C) was performed in order to explore the dissolution mechanisms arising at moderate CO2 partial pressure (0.3 MPa). An increase of the total porosity (φT) accompanied by a persistent permeability (k) decrease was measured. The mechanisms controlling this atypical anticorrelated k − φT relationship were investigated from the analysis of high-resolution X-ray microtomography images of the sample acquired before and after the experiment. All the evidences converge to the conclusion that the ubiquitous decrease of permeability measured during the 44 h of dissolution is due to the clogging of a fraction of the macroporosity by microporous material triggered by the rearrangement of the detached undissolved particles. This mechanism results in the development of low permeability zones bridging the macroporosity.
ISSN: 0094-8276

hal-00903585
https://hal.archives-ouvertes.fr/hal-00903585
DOI : 10.1002/grl.50595

Éditeur(s) : HAL CCSD Elsevier
Résumé : Deficient sealing in the well cement plugs and annulus due to mechanical fracturing is an important risk of CO2 leakage from the reservoir to others permeable layers and the surface. Such situation was reproduced at laboratory scale in order to determine the hydro-chemical control on the fracture permeability. Specifically, we investigated the effect of CO2 rich-brine flowing through fractured Portland cements at T = 60 °C and P = 10 MPa and variable flow rates. We showed that carbonation process is dominant and induces permeability decrease and leakage mitigation for extremely low flow rate whereas for high flow rate injection the permeability remains constant due to the precipitation of a low density secondary Si-rich phase which maintains the initial fracture aperture. At intermediate flow rate the hydraulic aperture can increase due to the densification of the material triggered by the net precipitation of low porosity calcite. These results emphasize that more complex behaviors than those considered from batch experiments may take place in the vicinity of flowing fractures. Specifically, the redissolution of the neoformed calcite as well as the development of amorphous phases, both controlled by the CO2-rich brine renewing rate in the fracture may prevent the healing fracture.
ISSN: 1750-5836

hal-00857555
https://hal.archives-ouvertes.fr/hal-00857555
DOI : 10.1016/j.ijggc.2013.04.002

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : Limestone dissolution by CO2 -rich brine induces critical changes of the pore network geometrical parameters such as the pore size distribution, the connectivity, and the tortuosity which govern the macroscopic transport properties (permeability and dispersivity) that are required to parameterize the models, simulating the injection and the fate of CO2 . A set of four reactive core-flood experiments reproducing underground conditions ( T=100∘C and P=12 MPa) has been conducted for different CO2 partial pressures (0.034
ISSN: 0169-3913

hal-00963597
https://hal.archives-ouvertes.fr/hal-00963597
DOI : 10.1007/s11242-013-0257-4

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : Coarse woody debris (CWD, dead wood sections a parts per thousand yen10 cm diameter) represents a large store of carbon in tropical forests; however, estimates of the flux of carbon from CWD in these forests remain poorly constrained. The objective of this study was to resolve the dry/wet season response of respiration in CWD (R (cwd)), and investigate the importance of biotic and abiotic factors for predicting the seasonal change of R (cwd) at the ecosystem level. This study presents a 4-month time series of R (cwd) measurements conducted on 42 dead trees (26 species) at the Paracou Research Station in French Guiana. R (cwd) measurements were repeated 13 times on each CWD sample from July to November 2011, spanning the transition from wet to dry season, and then from dry season to the following wet season. Seasonal drought caused monthly R (cwd) to drop by 20.5 +/- A 5.1% over the wet-dry transition. Changes in woody tissue moisture content explained 41.9% of the measured seasonal variability in R (cwd), but 60% of the seasonal variability in mean forest R (cwd) rates could be modelled using surface soil water content. We estimate that R (cwd) is approximately 5% of annual ecosystem respiration (R (eco)) and that seasonal variations in R (cwd) contribute appreciably to seasonal variations of R (eco), and should be included in functional models simulating the response of tropical rainforest ecosystems to current and future climate.
ISSN: 1432-9840

hal-01032431
https://hal.archives-ouvertes.fr/hal-01032431
DOI : 10.1007/s10021-013-9684-x

Éditeur(s) : HAL CCSD Wiley
Résumé :  
The lack of information on the ways seasonal drought modifies the CO2 exchange between Neotropical rainforest ecosystems and the atmosphere and the resulting carbon balance hinders our ability to precisely predict how these ecosystems will respond as global environmental changes force them to face increasingly contrasting conditions in the future. To address this issue, seasonal variations in daily net ecosystem productivity (NEPd) and two main components of this productivity, daily total ecosystem respiration (REd) and daily gross ecosystem productivity (GEPd), were estimated over 2 years at a flux tower site in French Guiana, South America (511605400N, 5215404400W). We compared seasonal variations between wet and dry periods and between dry periods of contrasting levels of intensity (i.e. mild vs. severe) during equivalent 93-day periods. During the wet periods, the ecosystem was almost in balance with the atmosphere (storage of 9.0 gCm_2). Seasonal dry periods, regardless of their severity, are associated with higher incident radiation and lower REd combined with reduced soil respiration associated with low soil water availability. During the mild dry period, as is normally the case in this region, the amount of carbon stored in the ecosystem was 32.7 gCm_2. Severe drought conditions resulted in even lower REd, whereas the photosynthetic activity was only moderately reduced and no change in canopy structure was observed. Thus, the severe dry period was characterized by greater carbon storage (64.6 gCm_2), emphasizing that environmental conditions, such as during a severe drought, modify the CO2 exchange between Neotropical rainforest ecosystems and the atmosphere and potentially the resulting carbon balance.
ISSN: 1354-1013

hal-01032067
https://hal.archives-ouvertes.fr/hal-01032067
DOI : 10.1111/j.1365-2486.2008.01610.x

Éditeur(s) : HAL CCSD Elsevier
Résumé : Adequate hydrogeophysical monitoring of CO2 geological storage remains a challenge as different parameters might be modified during storage. That implies to compare real-time measurements to an adequate baseline. At the Maguelone shallow experimental site a representative baseline for electrical resistivity was built from a large number of downhole geophysical measurements. At this coastal site this issue is particularly important due to the production of biogenic gas from the subsurface sediments. For this, a modified petrophysical model based on the Waxman-Smits model is proposed to estimate gas saturation found to vary from 2 to 7% within shallow sand layers.
ISSN: 1876-6102

hal-01412685
https://hal.archives-ouvertes.fr/hal-01412685
https://hal.archives-ouvertes.fr/hal-01412685/document
https://hal.archives-ouvertes.fr/hal-01412685/file/pezard2015.pdf
DOI : 10.1016/j.egypro.2015.07.910