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 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 American Association of Petroleum Geologists
Résumé : In reservoir engineering, hydrodynamic properties can be estimated from downhole electrical data using heuristic models (e.g., Archie and Kozeny-Carman's equations) relating electrical conductivity to porosity and permeability. Although proven to be predictive for many sandstone reservoirs, the models mostly fail when applied to carbonate reservoirs that generally display extremely complex pore network structures. In this article, we investigate the control of the three-dimensional (3-D) geometry and morphology of the pore network on the electrical and flow properties, comparing core-scale laboratory measurements and 3-D x-ray microtomography image analysis of samples from a Miocene reefal carbonate platform located in Mallorca (Spain). The results show that micrometer- to centimeter-scale heterogeneities strongly influence the measured macroscopic physical parameters that are then used to evaluate the hydrodynamic properties of the rock, and therefore, existing models might not provide accurate descriptions because these heterogeneities occur at scales smaller than those of the integration volume of the borehole geophysical methods. However, associated with specific data processing, 3-D imagery techniques are a useful and probably unique mean to characterize the rock heterogeneity and, thus, the properties variability.
ISSN: 0149-1423

hal-00950066
https://hal.archives-ouvertes.fr/hal-00950066
DOI : 10.1306/05221312134

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 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 Elsevier
Résumé : International audience
Coastal aquifers often display seawater intrusion resulting in the formation of a salty water wedge progressing inland. This study investigates the mass transfers in the mixing zone at the freshwater-seawater interface where the water is out of equilibrium with the rock-forming carbonates. Investigations were conducted in two boreholes, separated by 5 m, at the Ses Sitjoles test site (Mallorca Island, Spain) where repeated electrical conductivity logs of the formation and the saturating fluid, as well as regular pore-water sampling and permanent downhole multi-parameter monitoring of the water were performed over a period of 9 a. In the mixing zone, the significant acidification, the calcite saturation index profile and the Ca concentration profile cannot be explained by conservative mixing nor by dissolution-precipitation reactions only. Conversely, the analysis of organic C content and of the distinctly different time-resolved pH profiles measured in the two boreholes suggests the development of perennial biomass that triggers calcite dissolution. Moreover, the presence of biomass seems to be correlated with the permeability and vertical connectivity at the meter-scale. It is speculated that the mechanism could be self-activated because the microbiological activity induces calcite dissolution and tends to increase porosity and permeability that favors biomass development.
ISSN: 0883-2927

hal-00937665
https://hal.archives-ouvertes.fr/hal-00937665
DOI : 10.1016/j.apgeochem.2013.09.011

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 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 American Chemical Society
Résumé : Experiments were conducted to assess the potential impact of fractured well-cement degradation on leakage rate. Permeability was monitored while CO2-enriched reservoir-equilibrated brine was flowed at constant rate through a single fracture in a class G cement core under conditions mimicking geologic sequestration environments (temperature 60 °C, pressure 10 MPa). The results demonstrate that, at least for the conditions used in the experiment, an initial leakage in a 42 μm aperture fracture (permeability = 1.5 × 10-10 m2) can be self-mitigated due to the decrease of the fracture hydraulic aperture after about 15 h. This decrease results from the development of continuous highly hydrated amorphous Si-rich alteration products at the edge of the fracture and the dense carbonation of the bulk cement that mitigate the penetration of the alteration front.
ISSN: 0013-936X

hal-00950088
https://hal.archives-ouvertes.fr/hal-00950088
DOI : 10.1021/es401317c

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
Résumé : International audience
Understand the dynamics of the fresh-salt water interface in aquifers is a key issue to comprehend mixing processand to quantity the discharge of nutrients in to coastal areas. In order to go beyond the current knowledge inthis issue an experimental site has been set up at the alluvial aquifer Riera Argentona (Barcelona – Spain). Thesite comprises 16 shallow piezometers installed between 30 and 90 m from the seashore, with depths rangingbetween 15 and 25 meters. The seawater interface is being monitored using several techniques, the combinationof which will help us to understand the spatial and temporal behaviour of the mixing zone and the geochemicalprocesses occurring there. Specially the deepest piezometers are equipped with electrodes in order to performcross-hole electrical resistivity tomography (CHERT). In addition, all piezometers are also equipped with FiberOptic cable to perform distributed temperature measurements. Two single steel armoured fibre optic cable lines ofaround 600m length were installed in all boreholes. The objective is to use the cable both as passive and activetemperature sensor. The first is being done for the continuous monitoring of temperature whereas; the secondprovides a higher temperature resolution used to monitor field experiments.Periodic CHERT measurements are carried out between the piezometer equipped with electrodes, resultingin parallel and perpendicular vertical cross sections of the site resistivity. The position of the fresh-salt waterinterface can be identified due to the resistivity contrast between the saline and fresh water. Preliminary resultsof periodic distributed temperature measurements will be also be used to monitor the position of the mixing zonethanks to the contrast and seasonal temperature changes. Periodic down-hole EC profiles will be used to validatethe method.AcknowledgementsThis work was funded by the projects CGL2013-48869-C2-1 y CGL2013-48869-C2-2-R of the Spanish Government.We would like to thank SIMMAR (Serveis Integrals de Manteniment del Maresme) and the ConsellComarcal del Maresme in the construction of the research site
European Geosciences Union General Assembly 2016
Vienne, Austria

insu-01308757
https://hal-insu.archives-ouvertes.fr/insu-01308757

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 : 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 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 CRC Press Taylor & Francis Group
Résumé : aucun
Water-Rock Interaction XIII

hal-00857370
https://hal.archives-ouvertes.fr/hal-00857370

Éditeur(s) : HAL CCSD CRC Press Taylor & Francis Group
Résumé : In the chapter : Role of water-rock-gas interaction in sequestration of CO2
Water-Rock Interaction XIII

ISBN : 978-0415604260
hal-00855782
https://hal.archives-ouvertes.fr/hal-00855782

Éditeur(s) : HAL CCSD
Résumé : International audience
The porosity (from values of <1% up to more than 50%, with a mean value of 36.5%) and permeability (from very low values to 20.4 D, with a mean value around 800 mD) of 38 plugs, with a diameter 40 mm, have been measured. These plugs were taken approximately every 1.5 m along a 100 m-long core, sampling a series of reefal carbonate platform lithofacies. A non-unique relationship between porosity and permeability is obtained. In addition, the porosity was measured from processing X-ray micro-tomography images with resolutions ranging from 0.42 to 190.0 µm and sampling volumes ranging from less than 1 µm3 to few cm3. Depending on the structure of the pore network, the computed porosity is, in some cases, controlled by the X-ray image resolution and the sampled volume. While high resolution is required to image micro-porous material, large samples with lower resolution images are necessary for identifying distributed vugs and millimetre-scale structures. This study shows that multi-resolution X-ray micro-tomography is an effective tool for characterizing the multi-scale pore structure of carbonate rocks and understanding how it may control key petrophysical parameters such as porosity and permeability.
Geological Society Special Publication

hal-01174157
https://hal.archives-ouvertes.fr/hal-01174157
DOI : 10.1144/SP406.12

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Heletz sandstone (Israel) reactivity is studied by means of CO2-rich brine percolation experiments and modeling. Experiments are performed at in situ temperature and pressure conditions with two distinctly different injection flow rates and for two different brine compositions: the genuine Heletz brine and a similar brine but in equilibrium with gypsum. The Heletz sandstone is composed of quartz, dolomite, ankerite, K-feldspar, clay minerals and minor amounts of gypsum and pyrite. The main reaction is the dissolution of the carbonates which is fastest for the highest flow rate injection and for the genuine Heletz brine. Permeability increases during the five percolation experiments, regardless of flow rate and brine type. This increase in permeability is associated to a decrease in porosity during the gypsum-equilibrated brine experiments due to gypsum precipitation. The precipitation of secondary minerals (kaolinite, muscovite and smectite) is mainly controlled by the dissolution of K-feldspar and largest at low flow rate injection, indicating that these precipitation processes are diffusion-controlled and localized in immobile zones where favorable chemical micro-environments exist. These processes are quantified by means of a reactive transport model. These results indicated that the CO2 injection at the Heletz site should trigger both permeability increase in interface between brine and CO2, which may extend over a large extension and where mixing processes are very active, especially near the well under intermittent injection conditions.
ISSN: 1750-5836

hal-01356329
https://hal.archives-ouvertes.fr/hal-01356329
DOI : 10.1016/j.ijggc.2015.10.023

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