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 Oldendorf/Luhe
Résumé : International audience
Non-calcifying photosynthetic anthozoans have emerged as a group that may thrive under high carbon dioxide partial pressure (pCO(2)) conditions via increased productivity. However, the physiological mechanisms underlying this potential success are unclear. Here we investigated the impact of high pCO(2) on the dissolved inorganic carbon (DIC) use in the temperate sea anemone Anemonia viridis. We assessed the impacts of long-term exposure to high pCO(2), i.e. sampling in situ natural CO2 vents (Vulcano, Italy), and short-term exposure, i.e. during a 3 wk controlled laboratory experiment. We focused on photo-physiological parameters (net photosynthesis rates, chlorophyll a content and Symbiodinium density) and on carbonic anhydrase (CA) activity, an enzyme involved in the energy-demanding process of DIC absorption. Long-term exposure to high pCO(2) had no impact on Symbiodinium density and chlorophyll a content. In contrst, short-term exposure to high pCO(2) induced a significant reduction in Symbiodinium density, which together with unchanged net photosynthesis resulted in the increase of Symbiodinium productivity per cell. Finally, in both in situ long-term and laboratory short-term exposure to high pCO(2), we observed a significant decrease in the CA activity of sea anemones, suggesting a change in DIC use (i.e. from an HCO3- to a CO2 user). This change could enable a shift in the energy budget that may increase the ability of non-calcifying photosynthetic anthozoans to cope with ocean acidification.
ISSN: 0171-8630

hal-01546163
https://hal.archives-ouvertes.fr/hal-01546163
DOI : 10.3354/meps11916

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
The dissolution of carbonate rocks usually leads to both porosity (ϕ) and permeability (k) increase. We present experimental evidences and physical-based models of positive and anti-correlated dynamics of k and ϕ observed during dissolution experiments of carbonate rocks. We study the way the rate of change of ϕ and k is controlled by the degree of undersaturation of the percolating solution for two different types of carbonate rocks. We document the occurrence of an anti-correlated k−ϕ trend when the flowing fluid (deionized water) has a weak capacity of dissolution. A positive correlation is found when CO2 is added to the deionized water to increase the potential dissolution rate. Detailed analyses of the microstructures of the rock performed by X-ray microtomography reveal that low dissolution rate favors detachment of solid particles and their subsequent accumulation at the pore-throat inlet. Particles are detached from the rock matrix due to the differential dissolution rate of the indurated grains and the microporous cement. We then propose a simple phenomenological model to interpret the effect of the pore-throat clogging by the accumulation of partially dissolved carbonate particles. We conjecture that permeability is controlled by the decrease of the effective hydraulic radius and the increase of the tortuosity due to partial and localized obstruction of the pore network. Conversely, increasing the level of undersaturation of the flowing solution leads to an augmented potential of dissolving most of the transported particles before they reach the throats. In this case, both k and ϕ increase and display power-law correlations.
ISSN: 0169-3913

hal-01174145
https://hal.archives-ouvertes.fr/hal-01174145
DOI : 10.1007/s11242-015-0456-2

Éditeur(s) : HAL CCSD IWA Publishing
Résumé : International audience
UV spectrophotometry is largely used for water and wastewater quality monitoring. The measurement/estimation of specific and aggregate parameters such as nitrate and dissolved organic carbon (DOC) is possible with UV spectra exploitation, from 2 to multi wavelengths calibration. However, if nitrate determination from UV absorbance is known, major optical interferences linked to the presence of suspended solids, colloids or dissolved organic matter limit the relevance of UV measurement for DOC assessment. A new method based on UV spectrophotometric measurement of raw samples (without filtration) coupling a dual pathlength for spectra acquisition and the second derivative exploitation of the signal is proposed in this work. The determination of nitrate concentration is carried out from the second derivative of the absorbance at 226 nm corresponding at the inflexion point of nitrate signal decrease. A short optical pathlength can be used considering the strong absorption of nitrate ion around 210 nm. For DOC concentration determination the second derivative absorbance at 295 nm is proposed after nitrate correction. Organic matter absorbing slightly in the 270-330 nm window, a long optical pathlength must be selected in order to increase the sensitivity. The method was tested on several hundred of samples from small rivers of two agricultural watersheds located in Brittany, France, taken during dry and wet periods. The comparison between the proposed method and the standardised procedures for nitrate and DOC measurement gave a good adjustment for both parameters for ranges of 2-100 mg/L NO3 and 1 30 mg/L DOC. (C) 2016 Elsevier Ltd. All rights reserved.
ISSN: 0043-1354

hal-01460742
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01460742
DOI : 10.1016/j.watres.2016.11.010
PUBMED : 27838025

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 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 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
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 Springer Verlag
Résumé : International audience
The New Jersey continental shelf extends 150 km off the shoreline. During IODP Expedition 313, siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631, 669 and 755 m below seafloor at sites 27A, 28A and 29A respectively in very shallow waters (33.5 to 36 m depth). Pore water salinities display multilayered brackish-salty-brine units 10 to 170 m thick, where low-salinity water is preferentially stored in fine-grained sediments. The sharp boundaries of these buried aquifers are often marked by cemented layers a few centimetres thick. The mineralogy and scanning electron microscope observations of these layers show two phases of cementation by authigenic minerals: (1) the early carbonate cement is frequently associated with pyrite, and (2) the late silicate cement infills the residual porosity. The isotopic compositions of the carbonate cements vary widely: −2.4 < δ¹⁸O ‰ VPDB < +2.8; −15.1 < δ¹³C ‰ VPDB < +15.6. The δ¹⁸O values indicate that the carbonate cements precipitated with pore waters comprising variable mixtures of seawater and ¹⁸O-depleted fresh water originating from submarine groundwater discharge. The δ¹³C values of the carbonate cements are related to organic matter diagenesis, providing ¹³C-depleted dissolved inorganic carbon during bacterial sulphate reduction and anaerobic oxidation of methane, and ¹³C-rich dissolved inorganic carbon during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO²-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The estimated range of temperature (18±4 °C) during carbonate precipitation is consistent with carbonate cementation at moderate burial depths; however, silicate cementation occurred later during diagenesis at deeper burial depths.
ISSN: 0276-0460

hal-01559985
https://hal.archives-ouvertes.fr/hal-01559985
DOI : 10.1007/s00367-017-0506-6

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
Carbonation of peridotite is a widespread process in nature, with emerging societal and environmental implications through geological storage of CO2. We studied the micro- and nano-scale structures associated with the carbonation of peridotite pervaded by a CO2-rich water and the induced changes of its hydrodynamic properties. Focused ion beam (FIB) nanotomography was coupled with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. An experimental sample of dunite core percolated by a CO2-rich fluid (pCO2 = 11 MPa) at 160 °C was compared with a naturally carbonated sample from the Atlantic Ridge (Exp. IODP 304). Results of the 8-days percolation experiment show continuous alteration of olivine into magnesite locally associated with a poorly crystalline serpentine-type mineral referred to as proto-serpentine. The experiment is also characterized by an overall decrease in rock porosity (from 7.7 to 6.4%) and permeability (from 8.5 × 10− 16 to 1.7 × 10− 16 m2). The primary inter-granular porosity (1 to 10 μm) is progressively filled with magnesite, leading to the overall decrease of permeability. At the same time, a secondary small-scale porosity (10 nm to 1 μm) is created at the tip of the dissolution features along the (010) cleavage planes of olivine grains. Carbonate crystals grow within these etch-pit structures behind the dissolution front. Dissolution and precipitation occur at a relative rate that maintains the secondary porosity over the timescale of the experiment (i.e. carbonate growth has to be the slowest one). This process is interpreted as an interface coupled dissolution-precipitation mechanism of olivine carbonation. Proto-serpentine is only formed in highly reduced flow areas, such as small olivine etch-pits (10 to 500 nm wide), which are more isolated from CO2 input. SEM-FIB analyses show the 3D preferential orientation of the dissolution-precipitation planes within a given olivine grain. It suggests the formation of lateral connections between the etch-pits (infra-micrometric “channels”) providing access to reactants and removing reaction products at the reaction sites. The experimental results show that olivine dissolution and magnesite precipitation converge to a quasi-steady state resulting in a constant carbonation rate controlled by reaction kinetics and not by mass transfer for this flow regime. The system self-regulates, independently of the porosity change at least during this incipient stage of olivine carbonation. Similar textures are observed in natural samples collected at 170 m-depth in the vicinity of veinlets driving late fluids down into the cooling oceanic lithosphere. This suggests that similar mechanisms are active in nature and can play an important role in the late, low temperature alteration stages of fractured peridotite. These results also highlight the critical role of nm-scale spatial arrangement of dissolution and precipitation features on mass transfers and on the sustainability of olivine carbonation through coupled dissolution-precipitation processes.
ISSN: 0009-2541

hal-01684733
https://hal.archives-ouvertes.fr/hal-01684733
DOI : 10.1016/j.chemgeo.2017.11.013

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
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
Résumé : The heterogeneous nature and sometimes karstified carbonate environments has a direct impact on many environmental issues, such as coastal aquifers affected by saltwater intrusion. At the south of the island of Mallorca (Spain), the Llucmajor carbonate platform offers a privileged site for the study of such intrusions including the experimental site of Campos who meets the intrusion at shallow depth. The characterization of heterogeneous properties passes through a preliminary description of the properties of carbonate reservoirs, including those of the porosity. According to the wide range of sizes of heterogeneities from micrometer to hundreds of meters, the use of multiscale methods is required. This thesis focused on the determination of multiscale porosities from the microporosity to karstic porosity, and of relationships between observation scale changes of these properties. At the micron scale, high-resolution X-ray microtomography allows to extract the microporosity and the microporous network connectivity. At lower resolution (mm), X-ray tomography is also used to study the micro- and macro-porous network at the core scale which is already allocated to number of observations and measurements, including petrophysical. At the borehole scale, the wall images are used to identify the dissolved zones from centimeter macropores to plurimetric karstic cavities. At the larger scale, surface geophysics study the lateral extension of the karsts and heterogeneities. Finally, the porous structure of the studied site is integrated with its wide range of scales into the regional geology of the Llucmajor platform. Thus, the hydrogeophysical observatory set up on the site of Campos to monitor the spreading of salt water in the aquifer is integrated in its geological and petrophysical context, in order to refine the interpretation of its variations of salinity measurements during the time.
La nature hétérogène et parfois karstifiée des milieux carbonatés a un impact direct sur nombre de problématiques environnementales, comme celle des aquifères côtiers affectés par une intrusion d'eau salée. Au sud de l'ile de Majorque (Baléares, Espagne), la plate-forme carbonatée de Llucmajor offre un site privilégié pour l'étude de telles intrusions notamment avec le site expérimental de Campos, qui rencontre l'intrusion à faible profondeur. La caractérisation des propriétés hétérogènes du réservoir passe par une description préalable des propriétés des réservoirs carbonatés et notamment celle de la porosité. Au regard de la large gamme d'échelles d'hétérogénéités allant du micromètre à la centaine de mètre, l'utilisation de méthodes multi-échelles est nécessaire. Ce travail de thèse a porté sur la caractérisation multi-échelle de la porosité, allant de la microporosité à la porosité karstique, et l'établissement de relations entre les changements d'échelles d'observation de ces propriétés. A très petite échelle, la microtomographie haute-résolution à rayons X extrait à l'échelle du micron la microporosité et la connectivité des réseaux microporeux. A plus basse fréquence (celle du mm), la tomographie est également utilisée afin d'étudier le réseau micro- et macroporeux à l'échelle des carottes, à laquelle sont réalisées nombre d'observations et de mesures, notamment pétrophysiques. A l'échelle du puits, les images de paroi permettent d'identifier les zones de dissolution allant des macropores centimétriques aux cavités karstiques plurimétriques. A plus grande échelle, la géophysique de surface permet d'étudier l'extension latérale de ces karsts et hétérogénéités. Enfin, la structure poreuse du site étudié sur cette vaste gamme d'échelles est intégrée à la géologie régionale de la plate-forme de Llucmajor. Ainsi, l'observatoire installé sur le site pour surveiller la propagation de l'eau salée dans l'aquifère a pu être replacé dans son contexte géologique et pétrophysique, afin d'affiner l'interprétation de ses mesures de variations de salinité au cours du temps.
https://tel.archives-ouvertes.fr/tel-00633488

tel-00633488
https://tel.archives-ouvertes.fr/tel-00633488
https://tel.archives-ouvertes.fr/tel-00633488/document
https://tel.archives-ouvertes.fr/tel-00633488/file/TheseHebert.pdf

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
Résumé : This work focus on the characterization of the source and dynamic of compactional fluids during sedimentary burial, through two complementary examples of late orogenic oil‐field half‐grabens: The exhumed Lodève Permian Basin and a deep buried Jurassic basin in the North Viking Graben (North Sea).Constituting the main part of the thesis, a multi‐disciplinary approach was conducted in the Lodève Basin where Ba‐F‐Cu‐Pb polymetallic mineralized systems are trapped into synrift faults and paleokarsts in the carbonate basement at the hinge point of the rollover. The source, timing and P/T conditions of fluid migration were deduced from the analysis of the microfabric, the fluid inclusions microthermometry, and the isotopic (Sr, S, O, H) and Rare Earth Element (REE) signature. Results are then crossed with a structural and thermal modeling that consolidates the sequence and dynamics of fluid during burial.A similar approach was conducted in the North Viking Graben where fluid markers are restricted to 3D seismic and well core data. Comparable Ba‐Pb‐Zn veins are reported in basin margin, plugging one of the most important siliciclastic hydrocarbon reservoir in the substratum. This analysis provides additional constraints on basinal fluid behavior and allows us to propose a global dynamic model for various compositions of fluids and reservoirs.We conclude to a polyphase fluid sequence history including:(a) In the carbonate basement of the Lodève Basin, karstic paleocanyon incisions and associated cavities coupled to synrift fault, act as major drain for fluids. These structures are early affected by hypogen‐sulfuric karstification in response to the interaction between bacterial oxidation of sulfides entrapped within Lower Permian blackshales and the basement oxidizing aquifer.(b) Disequilibrium compaction initiates overpressure‐driven basinal fluid migration towards basin margins, characterized by temperatures around 150‐180°C and salinities between 9 et 18wt%eq.NaCl. Isotopic (Sr, S, O) and REE analyses reveal that Ba‐M+‐rich mineralizing fluids derived mainly from buried blackshales diagenesis. External fluids coming from the lower crust are also identified that play a key role in fluorite precipitation by the leaching of late hercynian granites (mean temperature of 250°C and salinity > 20wt%eq.NaCl).(c) During the synrift period, fluid overpressure is responsible for the periodic reactivation of fault plane according to seismic‐valve process, bedded‐control shearing and hydraulic brecciation at the basement‐seal interface. These mechanisms induce cyclic polymetallic mineralization by the mixing between in‐situ formation water and deep ascending basinal fluids.(d) Thermogenic fluids expulsion starts with last basinal fluids during late burial stage. Hydrocarbons thus migrate along the same regional pathways up to the rollover crest, where they are partly rerouted by the previous mineralized baffle.(e) In the Lodève basin, post‐rift exhumation of the margins led to the remobilization of synrift deposits by subaerial biochemical processes at the sulfate‐methane transition. The latter results from the interaction between the still active hydrocarbon dysmigration with a playa lake sulfate‐rich aquifer. Secondary low‐temperature barite fronts precipitate then within basement meteoric karsts.In addition to the « source to sink » model of basinal fluids, this work provides new insights on the early plugging of hydrocarbon reservoirs and for the metallogenesis of Mississippi Valley‐Type deposits.
Ce travail porte sur la caractérisation de la source et de la dynamique des fluides de bassin au cours de leur chargement à travers deux exemples complémentaires de demi‐grabens tardi‐orogéniques pétroliers : Le Bassin Permien de Lodève, aujourd’hui à l’affleurement et un bassin jurassique enfouis dans le North Viking Graben (Mer du Nord).Le coeur de la thèse concerne le Bassin de Lodève où, à partir d’une approche pluridisciplinaire intégrée, nous avons caractérisé l’architecture des minéralisations (Ba, F, Cu, Pb) piégées dans un réseau paléokarstique alimenté par les failles syn‐rift, dans le substratum carbonaté à l’apex du roll‐over. La source, le calendrier et les conditions de migration des fluides ont été approchés à partir de l’analyse de la micro‐fabrique, la microthermométrie sur inclusions fluides, les analyses isotopiques (Sr, S, O, H) et de Terres Rares. Les résultats analytiques ont été enfin croisés avec un modèle thermique et structural du bassin qui conforte la séquence et la dynamique du système fluide en cours d’enfouissement.Une démarche similaire, mais plus limitée, a été conduite dans le bassin du North Viking Graben où l’accès aux marqueurs fluides est restreint aux données de sismique 3D et de carottes. Comme à Lodève, les minéralisations Ba‐Pb‐Zn colmatent un réservoir dans le substratum à l’apex du roll‐over. Elles se présentent sous forme de ciments dans des grès ou des fractures. Cette analyse apporte des contraintes complémentaires et permet de proposer un modèle dynamique général avec des variantes en fonction de la nature des fluides et des réservoirs.On retiendra donc la séquence fluide suivante :(a) Dans le cas du bassin de Lodève sur substratum carbonaté, les chemins préférentiels de drainage se développent dans des paléocanyons N‐S couplés à un réseau de fractures et d’endokarsts météoriques. Ces derniers sont élargis en début de rifting par la dissolution hypogène sulfurique produite par l’oxydation bactérienne des sulfates et des pyrites des blackshales, au contact de l’aquifère oxydant du Cambrien.(b) Le déséquilibre de compaction initie la migration des fluides interstitiels en surpression vers les marges avec des températures autour de 150‐180°C et des salinités entre 9 et 18wt%eq.NaCl. Les analyses isotopiques (Sr, S, O) révèlent que la majorité des fluides provient de l’altération diagénétique des blackshales riches en métaux. Des interactions sont également mises en évidence avec des fluides profonds (entre 240°C et 260°C ; salinités > à 20wt%eq.NaCl), qui lessivent les granites tardi‐hercyniens.(c) Pendant le syn‐rift, les conditions de surpression de fluide permettent la réactivation cyclique des failles, les décollements stratigraphiques et la formation de brèches hydrauliques, favorisant la mise en connexion avec les réservoirs superficiels à l’apex du rollover. Le modèle de Sibson ajusté aux fluides de bassins est alors le moteur de la migration verticale.(d) Les fluides thermogéniques commencent à être expulsés avec les derniers fluides de compaction au cours d’un stade plus évolué de l’enfouissement en empruntant les mêmes chemins jusqu’à l’apex du roll over. Ils sont alors partiellement freinés et déviés par les colmatages minéralisés antérieurs.(e) A Lodève, la continentalisation des minéralisations antérieures au cours de l’exhumation post‐rift conduit à leur remaniement partiel au niveau de la transition sulfate‐méthane induite par l’interaction entre une playa évaporitique et la dysmigration des hydrocarbures. Des barytines secondaires de basse température, déprimées en Sr sont alors précipitées de manière synsédimentaire dans des karsts météoriques du socle.Outre l’illustration d’un modèle complet (source to sink) de dynamique des fluides dans un bassin, ce travail apporte de nouvelles contraintes dans l’approche du colmatage des réservoirs à hydrocarbures sur les têtes de blocs basculés et sur la genèse des gîtes miniers de type Mississippi Valley‐Type.
https://hal.archives-ouvertes.fr/tel-01457583

tel-01457583
https://hal.archives-ouvertes.fr/tel-01457583
https://hal.archives-ouvertes.fr/tel-01457583/document
https://hal.archives-ouvertes.fr/tel-01457583/file/th%C3%A8seLaurent2015V2.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study presents the geochemical composition of superficial sediment under oxic and suboxic bottom water conditions along the Chilean continental margin (SE Pacific), where evidence for benthic chemosynthetic activity associated with diffuse seeping of chemically reduced fluids has been reported. The exploration was carried out at: (1) the Chilean Triple Junction (CTJ), at a water depth of ∼2900 m, with the additional indication of hydrothermal activity near a methane-rich cold-seep area (46°S) (German et al., 2010); and (2) the El Quisco methane seep site (EQSS), at ∼340 m water depth (33°S) (Melo et al., 2007; Krylova et al., 2014). While the deeper CTJ is located within an oxic environment (dissolved oxygen in the bottom waters: 164 μM), the shallower EQSS lies within a suboxic environment (dissolved oxygen in bottom water: 23 μM), located within the lower limit of the SE Pacific oxygen minimum zone (OMZ).Pore water from short cores was analyzed for dissolved major, minor, and trace elements (Cl, Na, Mg, K, Ca, Sr, Si, B, P, Ba, Pb, Mn, Fe, Cd, U, and Mo), δ13DIC, sulfide, sulfate, and methane. The solid sediment fraction was likewise analyzed for total organic carbon (TOC), metals, and redox potential. Elevated sediment temperatures were found in superficial sediments (5–13 °C) at the CTJ site, which could be due to warm fluids associated with the proximity of the ridge, where hydrothermal vents may occur. Reduced fluids were also present here, indicated by higher Mn fluxes toward the water column even in oxidized sediments (RPD > 8 cm), which contrasted with the lower fluxes in reduced sediments of the EQSS site (RPD ∼ 2 cm). 13C-depleted DIC, anomalously low pore water Cl (∼15 ppb), and low concentrations of other major elements may be the result of dilution by fluid seeping and precipitation of major elements, producing authigenic enrichment (Ca, Mg, Sr). The fluid could also: (a) be diluted by pure water produced during methane hydrate dissociation, as observed in other cold-seep areas; and (b) correspond to clay mineral dehydration, as reported in plate subduction systems. The reducing conditions established at the CTJ conduct the Cd enrichment at a similar magnitude of that seen at the shallower suboxic site (EQSS). Evidence of chimney or vent fauna was not observed. At the EQSS, higher TOC and total sulfide contents were consistent with enhanced deposition of organic matter and reducing conditions developed in the OMZ, favoring the authigenic enrichment of Cd, U and Pb. The geochemical evidence, based only on methane concentrations and δ13DIC, is insufficient to establish the presence of methane seeps, as previously reported.
ISSN: 0079-6611

hal-01412700
https://hal.archives-ouvertes.fr/hal-01412700
DOI : 10.1016/j.pocean.2016.09.002

Éditeur(s) : HAL CCSD
Résumé : International audience
The most active deep convection area in the western Mediterranean Sea is located in the Gulf of Lions. Recent studies in this area provides some insights on the complexity of the physical dynamics of convective regions, but very little is known about their impacts on the biogeochemical properties. The CASCADE (CAscading, Surge, Convection, Advection and Downwelling Events) cruise, planed in winter 2011, give us the opportunity to compare vertical profiles of properties sampled either during stratified conditions or after/during a convection event. In the present study, we focus on the distributions of the carbonate system properties (mainly total alkalinity, AT; and total dissolved inorganic carbon, CT) because, in the context of the climate change, deep convection areas are suspected to significantly increase the sequestration of anthropogenic CO2 (CANT). Given its limited size, the impact of the Mediterranean Sea on the global carbon budget is probably minor but this marginal sea can be used as a laboratory to better understand carbon sequestration and its transfer to the basin interior by deep convection processes. Distributions of AT and CT, both measured from bottle samples, and that of CANT (estimated with the TrOCA approach) are first analyzed in the light of other key properties (salinity, temperature, and dissolved oxygen). An objective interpolation procedure is then applied to estimate CT and AT from CTD measured properties. With this procedure, the vertical resolution goes from a maximum of 32 samples per station to one property estimate every meter (more detailed distributions are obtained). Results provide arguments to conclude that CANT is rapidly transferred to the deepest layer due to deep convection events. During deep convection events, the increase of CANT in the water column is positively correlated to that of potential density and oxygen content. The challenge of quantifying the amount of sequestered carbon is however not resolved due to the complexity and the highly dynamical nature of the convective regions. Deep convection in the Gulf of Lions, in parallel with cascading along the continental slope, could thus potentially explain the very high levels of both CANT and acidification estimated in the deep layers of the western Mediterranean Sea.
Deep Sea Research Part I: Oceanographic Research Papers

hal-01336725
https://hal-univ-perp.archives-ouvertes.fr/hal-01336725
DOI : 10.1016/j.dsr.2016.04.003

Éditeur(s) : HAL CCSD
Résumé : In coastal carbonate aquifers submitted to a saline intrusion, water - rock interactions processes at the interface between freshwater and saltwater are a cause for heterogeneities development within the porous media. The dissolutions and precipitations induced by the mixing zone play a major role in the transport properties of the reservoir and so in the long term evolution of the saltwater intrusion. The characterization and the in situ observation of a current saline intrusion in the Llucmajor carbonate platform at the experimental site of Ses Sitjoles (South-Easth of Mallorca Island, Spain), allowed to study the temporal evolution of the saltwater intrusion and the biogeochemical processes active in the mixing zone. The influence of microstructure, characterized using X-Ray microtomography, on the petrophysical and flow properties was investigated in laboratory and flow-through experiments were also conducted to study the modifications of the microstructures when submitted to water - rock interactions processes. The mixing zone at the Ses Sitjoles site appears as quite thick and not very sensitive to climate and anthropic stress and is proved to be the locus of active microbiological activity. Laboratory studies highlight a strong control of the microporosity on transport processes and of pCO2 on water - rock interactions. The percolation experiments of slightly reactive waters reveal calcite dissolution together with a decrease in permeability due to a rearrangement of micro-grains within the microporous network.
Les processus d'interactions fluide-roche à l'interface eau douce-eau salée, dans les aquifères carbonatés côtiers soumis à une intrusion saline, sont une des causes du développement d'hétérogénéités dans la structure du milieu poreux. Les dissolutions et/ou précipitations engendrées par la présence de cette zone de mélange jouent un rôle déterminant pour les propriétés de transport du réservoir et donc l'évolution à long terme de l'intrusion d'eau salée. En prenant l'exemple de la plateforme carbonatée de Llucmajor au niveau du site expérimental de Ses Sitjoles (Sud-Est de Majorque, Espagne), un travail de caractérisation et d'observation in situ à moyen terme de l'intrusion saline actuelle de ce réservoir permet de décrire son évolution temporelle et les processus biogéochimiques actifs dans la zone de mélange. L'influence de la microstructure du milieu poreux, caractérisée par microtomographie RX, sur les propriétés pétrophysiques et hydrodynamiques est étudiée en laboratoire et des expériences de percolations d'eaux réactives (mélanges eau douce - eau salée et eau pure chargée en CO2) sont réalisées afin d'étudier les modifications de ces microstructures lorsqu'elles sont soumises à des interactions eau - roche. La zone de mélange eau douce - eau salée rencontrée au niveau du site de Ses Sitjoles est large et peu sensible aux contraintes extérieures (climatologiques et anthropiques) et constitue un lieu d'activité microbiologique particulièrement actif. En laboratoire, on observe un fort contrôle des phénomènes de transport par la microporosité et des processus d'interactions eau - roche par la pCO2. Dans le cas d'une percolation de fluides moyennement réactifs, les expériences mettent en évidence une dissolution de calcite accompagnée par une diminution de la perméabilité, liée à un réarrangement des micro-grains à l'intérieur du réseau microporeux.
https://tel.archives-ouvertes.fr/tel-00767152

tel-00767152
https://tel.archives-ouvertes.fr/tel-00767152
https://tel.archives-ouvertes.fr/tel-00767152/document
https://tel.archives-ouvertes.fr/tel-00767152/file/thesegaring.pdf

Éditeur(s) : HAL CCSD AGU and the Geochemical Society
Résumé : International audience
[1] Large changes in magnetic mineral concentration dependent parameters by more than 1 order of magnitude occur over 50–150 cm intervals in two marine sediment cores from the oxygen minimum zone in the Gulf of Aden. High-resolution sedimentological and chemical analyses indicate that these intervals are not associated with turbiditic events or sediment reworking, they do not result from changes in carbonate dilution or differences in sediment properties, and they do not correspond to volcanic layers. Magnetic mineralogical analyses reveal a change in magnetic mineral concentration from a magnetite-goethite assemblage to pure magnetite within the peak. The peaks almost disappear when the abundance of magnetic minerals is calculated after correcting for the magnetic moments of each magnetic mineral. Therefore, under the assumption that the variability of the magnetic parameters results from postdepositional mineralogical transformations, a relatively constant amount of magnetite was present at the surface of the sediment. Changes in redox conditions and nonsteady state diagenesis transformations have effectively been observed along both cores. Large values of total organic carbon coincide with poor preservation of biogenic and detrital magnetite, which reflects reductive dissolution of the finer magnetite grains. At the same levels, Fe 2þ release from reductively dissolved magnetite favored precipitation of goethite. The susceptibility peaks coincide with episodes of magnetite preservation caused by reduced surface
ISSN: 1525-2027

insu-01311064
https://hal-insu.archives-ouvertes.fr/insu-01311064
https://hal-insu.archives-ouvertes.fr/insu-01311064/document
https://hal-insu.archives-ouvertes.fr/insu-01311064/file/ggge2013-14-3779-bouilloux.pdf
DOI : 10.1002/ggge.20234