Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Several studies, both theoretical and experimental, show that sedimentary rocks have a fractal pore-grain interface. In this paper a computer simulated 3-D sedimentary rock structure generated by the Relaxed Ballistic Bidisperse Deposition Model (RBBDM), is investigated to characterize the micro structure of its pores. The pore volume and the rock-pore interface show the same fractal dimension indicating that the pore volume is a fractal. The two point density correlation is computed for the pore space and the results compare favourably with the range reported from experiments. An array of 2-D X-ray tomography micrograph sections of a real sedimentary rock, an oolitic limestone (pure calcite) from the Mondeville formation of Middle Jurassic age (Paris Basin, France), was used to generate a 3-D bitmap. The 3-D real rock sample generated in this manner, was analysed for similar studies as the simulated structure. The results were compared with those obtained from simulation. The simulation results agree qualitatively with the real rock sample. Diffusion through the connected pore space of the simulated structure was studied using a random walk algorithm and the results compared with the similar simulation study done on the 3-D oolitic limestone specimen. In both cases diffusion was found to be anomalous indicating that the sedimentary rock has a fractal geometry. The favourable comparability of results between the simulated and real rock supports the usefulness of the model of sedimentary rock generation which can be applicable to transport phenomena.
ISSN: 0956-540X

hal-00823061
https://hal.archives-ouvertes.fr/hal-00823061
DOI : 10.1093/gji/ggs084

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Predicting the impact of underground engineering on the environment requires the knowledge of natural media at different scales. In particular, understanding basic phenomena controlling the properties of rocks in the presence of complex fluids necessitates a detailed atomic description of the solid/fluid/solid contacts, the subject of Part I of the present study. First, building the solid interspace between two different crystals in a non-periodic situation is achieved using the ab initio and molecular mechanics code GenMol (TM). A description of the fluid confined within the interspace is then derived from the original genetic iterative multi-species (GIMS) algorithm implemented in the same code. This approach consists of equilibrating chemical potentials, cycle after cycle and species after species, between the confined fluid and the free natural fluid. An elementary iteration for a species k consists of different steps incrementing the number N-k of particles k, with other numbers N-k remaining constant. At each step, an optimum fluid composition is obtained by a genetic process distributing the fluid particles on a grid by stochastic shots, followed in fine by a refining process. The effectiveness of the GIMS approach is demonstrated in the case study of a fluid confined between two (0 0 1) kaolinite faces, with apertures h varying between 4 and 10 A. connected to a 9-species external solution [H2O, Cl-, Na+ CO2(aq), NaCl(aq), Ca2+, Mg2+, HCO3-, H3O+] where concentrations are ranging from 55 to 10(-4) mol/L. The results show a drastic variation in the solute/solvent and cations/ions ratios in the confined fluid when aperture h is lowered to less than 1 nm. These results obtained with a very rapid convergence of the iterative algorithm combined with a very competitive genetic optimizer are validated with high precision on a free solution. This description of contacts between crystals is original and unattainable by standard crystal interface approaches. It opens the way to understanding and/or predicting phenomena between crystals in a complex natural environment, such as adhesion or repulsion investigated in the Part II of this study.
ISSN: 0022-0248

hal-00544569
https://hal.archives-ouvertes.fr/hal-00544569
DOI : 10.1016/j.jcrysgro.2010.08.009

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 American Physical Society (APS)
Résumé : International audience
Diffusion in natural and engineered media is quantified in terms of stochastic models for the heterogeneity-induced fluctuations of particle motion. However, fundamental properties such as ergodicity and self-averaging and their dependence on the disorder distribution are often not known. Here, we investigate these questions for diffusion in quenched disordered media characterized by spatially varying retardation properties, which account for particle retention due to physical or chemical interactions with the medium. We link self-averaging and ergodicity to the disorder sampling efficiency Rn, which quantifies the number of disorder realizations a noise ensemble may sample in a single disorder realization. Diffusion for disorder scenarios characterized by a finite mean transition time is ergodic and self-averaging for any dimension. The strength of the sample to sample fluctuations decreases with increasing spatial dimension. For an infinite mean transition time, particle motion is weakly ergodicity breaking in any dimension because single particles cannot sample the heterogeneity spectrum in finite time. However, even though the noise ensemble is not representative of the single-particle time statistics, subdiffusive motion in q≥2 dimensions is self-averaging, which means that the noise ensemble in a single realization samples a representative part of the heterogeneity spectrum.
ISSN: 2470-0053

hal-01622668
https://hal.archives-ouvertes.fr/hal-01622668
https://hal.archives-ouvertes.fr/hal-01622668v2/document
https://hal.archives-ouvertes.fr/hal-01622668/file/russian2017.pdf
DOI : 10.1103/PhysRevE.96.022156

Éditeur(s) : HAL CCSD Oxford University Press (OUP): Policy P - Oxford Open Option A Oxford University Press (OUP)
Résumé : International audience
It is well known that sedimentary rocks having same porosity can have very different pore size distribution. The pore distribution determines many characteristics of the rock, among which its transport properties are often the most useful. Multifractal analysis is a powerful tool that is increasingly used to characterize the pore space. In this study, we performed multifractal analysis of pore distribution on simulated sedimentary rocks using the relaxed bidisperse ballistic deposition model (RBBDM). The RBBDM can generate a 3-D structure of sedimentary rocks of variable porosity by tuning the fraction p of particles of two different sizes. We also performed multifractal analysis on two samples of real sedimentary rock to compare with the simulation studies. One sample, an oolitic limestone is of high porosity (40 per cent) while the other is a reefal carbonate of low porosity, around 7 per cent. 2-D sections of X-ray microtomographs of the real rocks were stacked sequentially to reconstruct the real rock specimens. Both samples show multifractal character. The results from analysis of real rock agree quite well with the simulated structure of low porosity. The simulated rock of high porosity showed a weak multifractal nature though the real rock sample of similar porosity was found to be strongly multifractal. We propose a ‘structure parameter’ ξ which is a function of porosity and the generalized dimensions, and controls the transport properties of the rock.
ISSN: 0956-540X

hal-01174142
https://hal.archives-ouvertes.fr/hal-01174142
DOI : 10.1093/gji/ggu417

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
We present a set of single-well injection withdrawal tracer tests in a paleoreef porous reservoir displaying important small-scale heterogeneity. An improved dual-packer probe was designed to perform dirac-like tracer injection and accurate downhole automatic measurements of the tracer concentration during the recovery phase. By flushing the tracer, at constant flow rate, for increasing time duration, we can probe distinctly different reservoir volumes and test the multiscale predictability of the (non-Fickian) dispersion models. First we describe the characteristics, from microscale to meter scale, of the reservoir rock. Second, the specificity of the tracer test setup and the results obtained using two different tracers and measurement methods (salinity-conductivity and fluorescent dye­optical measurement, respectively) are presented. All the tracer tests display strongly tailed breakthrough curves (BTC) consistent with diffusion in immobile regions. Conductivity results, measured over 3 orders of magnitude only, could have been easily interpreted by the conventional mobile-immobile (MIM) diffusive mass transfer model of asymptotic log-log slope of 2. However, the fluorescent dye sensor, which allows exploring much lower concentration values, shows that a change in the log-log slope occurs at larger time with an asymptotic value of 1.5, corresponding to the double-porosity model. These results suggest that the conventional, one-slope MIM transfer rate model is too simplistic to account for the real multiscale heterogeneity of the diffusion-dominant fraction of the reservoir.
ISSN: 0043-1397

insu-00373695
https://hal-insu.archives-ouvertes.fr/insu-00373695
https://hal-insu.archives-ouvertes.fr/insu-00373695/document
https://hal-insu.archives-ouvertes.fr/insu-00373695/file/Gouze_et_al-2008-Water_Resources_Research.pdf
DOI : 10.1029/2007WR006278

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 Springer Verlag (Germany) Springer Verlag
Résumé : Direct numerical simulations of flow through two millimeter-scale rock samples of limestone and sandstone are performed using three diverse fluid dynamic simulators. The resulting steady-state velocity fields are compared in terms of the associated empirical probability density functions (PDFs) and key statistics of the velocity fields. The pore space geometry of each sample is imaged at 5.06−μm voxel size resolution using X-ray microtomography. The samples offer contrasting characteristics in terms of total connected porosity (about 0.31 for the limestone and 0.07 for the sandstone) and are typical of several applications in hydrogeology and petroleum engineering. The three-dimensional fluid velocity fields within the explicit pore spaces are simulated using ANSYS® FLUENT® ANSYS Inc. (2009), EULAG Prusa et al. (Comput. Fluids 37, 1193–1207 2008), and SSTOKES Sarkar et al. (2002). These computational approaches are highly disperse in terms of algorithmic complexity, differ in terms of their governing equations, the adopted numerical methodologies, the enforcement of internal no-slip boundary conditions at the fluid-solid interface, and the computational mesh structure. As metrics of comparison to probe in a statistical sense the internal similarities/differences across sample populations of velocities obtained through the computational systems, we consider (i) integral quantities, such as the Darcy flux and (ii) main statistical moments of local velocity distributions including local correlations between velocity fields. Comparison of simulation results indicates that mutually consistent estimates of the state of flow are obtained in the analyzed samples of natural pore spaces despite the considerable differences associated with the three computational approaches. We note that in the higher porosity limestone sample, the structures of the velocity fields obtained using ANSYS FLUENT and EULAG are more alike than either compared against the results obtained using SSTOKES. In the low-porosity sample, the structures of the velocity fields obtained by EULAG and SSTOKES are more similar than either is to the fields obtained using ANSYS FLUENT. With respect to macroscopic quantities, ANSYS FLUENT and SSTOKES provide similar results in terms of the average vertical velocity for both of the complex microscale geometries considered, while EULAG tends to render the largest velocity values. The influence of the pore space structure on fluid velocity field characteristics is also discussed.
ISSN: 1420-0597

hal-01174152
https://hal.archives-ouvertes.fr/hal-01174152
DOI : 10.1007/s10596-015-9486-7

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
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 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 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 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 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 Springer Verlag (Germany) Springer Verlag
Résumé : Production rates in horizontal shale gas wells display declines that are controlled by the low permeability and the intrinsic heterogeneity of the shale matrix. We present an original multi-continuum approach that yields a physical model able to reproduce the complexity of the decreasing gas rates. The model describes the dynamics of gas rate as function of the physical reservoir parameters and geometry, while the shale matrix heterogeneity is accounted for by a stochastic description of transmissivity field. From the 3D (Dimensional) problem setting, including the heterogeneous shale matrix, the fractures generated by the hydrofracking operations, as well as the production well characteristics, we establish an effective upscaled 1D model for the gas pressures in fracture and matrix as well as the volumetric flux. We analyse the decline curves behaviour, and we identify the time scales that characterize the dynamics of the gas rate decline using explicit analytical Laplace space solutions of the upscaled process model. Asymptotically, the flux curves decrease exponentially, while in an intermediate regime we find a power-law behaviour, in which the flux scales with a power law in time as (t^{-beta }), where (beta ) reflects the medium heterogeneity. We use this solution to fit a set of real data displaying distinctly different decline trends and study the sensitivity of the model to the reservoir parameters in order to identify their respective controls at the different stages of the decline curve dynamics. Results indicate that the initial value of the gas rate is determined by the transmissivity of the fractures and the initial pressure of the gas in the shale matrix. The latter causes mainly a shift in the entire decline curve. The early time of decline curve shape is primarily controlled by the fracture properties (compressibility and transmissivity). During the main part of the economically valuable production times, i.e. before the production rate drops exponentially, the decline curve is strongly controlled by the properties of the shale rocks including their heterogeneity, which is modelled by two parameters describing the non-Fickian pressure diffusion effects in a stochastic framework.
ISSN: 0169-3913

hal-01217247
https://hal.archives-ouvertes.fr/hal-01217247
DOI : 10.1007/s11242-015-0504-y

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : Results are reported for an acidic water flow-through experiment conducted in a fractured argillaceous limestone sample (73% carbonates). The change in fracture geometry and related parameters is reported for six data sets obtained from synchrotron X-ray microtomography experiments. High-resolution three-dimensional images of the sample allowed quantification of the changes in fracture morphology at a spatial resolution of 6 ;μm. Mineral mass loss and permeability changes in the sample were also determined. Several physico-chemical phenomena were identified during the experiment. Initial smooth fracture surfaces evolved rapidly toward rough surfaces with uneven clay coverage due to the preferential dissolution of carbonate minerals compared to clay minerals whose dissolution rate is about 106 slower. A microporous clay coating progressively developed at the fluid-rock interface during heterogeneous dissolution of the fracture, while the global dissolution rate of the fracture walls exponentially decreased. The increase in surface roughness and the presumed reorganization of clays caused a progressive reduction in permeability. During the last flow-through stage, a large decrease in sample permeability was attributed to the large removal of clay particles; this process was responsible for a dramatic collapse of the fracture walls near the sample inlet and led to the development of preferential flow pathways. The development of the clay coating also acted as a barrier to flow and mass transfer between calcite grains and bulk solution and affected transport processes within the fracture
ISSN: 0043-1397

hal-00405333
https://hal.archives-ouvertes.fr/hal-00405333
DOI : 10.1029/2006WR005379

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 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