Éditeur(s) : HAL CCSD
Résumé : The Franceville Basin (2.1 Ga) in southeastern Gabon, hosts a black shale series well preserved (FB Formation) which represents an exceptional example of unmetamorphised Paleoproterozoic sediment strata. This basin includes the protore of one of the largest Mn-oxide laterite ore worldwide, mined by Eramet-Comilog. The aim of this this work is to determine formation conditions of this protore and to characterize the global sedimentary evolution of the FB Formation which include the protore. This 75 m thick protore is constituted of Mn carbonate-rich black shales which represent a potential ore deposit for the future. It was drilled, on the Bangombé plateau, during a recent campaign of 24 boreholes with an average depth of 125 m.Through multidisciplinary study on these cores and key outcrops of the basin, this work focuses on : i) the depositional environment of the Mn-protore and FB Formation ; ii) the processes of formation of the Mn-carbonates at 2.1 Ga and iii) the architecture and distribution of Mn-rich levels of the protore on the Bangombé Plateau.A detailed sedimentological and petrological study allowed us to redefine the division of the FB into nine units, named U1 to U9 from the base to the top. These units show a fine upward cycle up to U5 and a reverse coarse loop until U9. This division leads to a new interpretation to propose an evolution from a shoreface depositional environment controlled by deltaic currents (U1) to an offshore depositional environment with anoxic conditions (U2). In this basin, a system of submarine fan is developed, feeding a network of sand injections (injectites) covering the Bangombé plateau (70 km²) and with a thickness of 150 m affecting U4 to U7, including the Mn-protore. The protore depositional environment formed below the wave base limit (U4, U5 and U6) in a starved basin, controlled by biochemical sedimentation allowed the formation of Mn-carbonates. The end of starved basin, would allow the re-opening of the detrital input into the offshore basin (U7). This basin is then filled by storm bar deposits intersected by deltaic sub-aquatic channels (U8). The U9 unit corresponds to a quiet lagoon environment, allowing the multicellular organism development for the first time on the planet.A geochemical study allowed the characterization of the depositional environment of Mn-carbonates as an anoxic to sub-oxic and alkaline environment. For the first time, we showed that the manganese carbonates, present as bacteriomorph forms, are precipitated from the seawater by the mediated photosynthetic cyanobacterial activity, which allows CO2 / HCO3 depression of the environment and a local increase of pH. The cyanobacterial activity is controlled by the absence of bottom currents, which increase the detrital input. This would stop the activity of the cyanobacteria and thus would lead to the decrease of the Mn-concentration along the protore.Finally, well-log and a sequential correlation analyses allowed us to detail spatial and timing repartition of FB Formation deposit, controlled by a tectono-sedimentary model. We propose two- tectono-sedimentary phases. A first syn-tectonic phase (U1 to U3) controls the depocentres and sedimentation gaps. Turbidite coarse deposits are located in the most subsident part, clay deposits rather on the slope and carbonates on shoals. A second post-tectonic phase (U4 to U7) allows isopach deposits. The Mn-protore formed during the post-tectonic phase. However, it shows a variable thickness due to subsidence to the north of the Bangombé plateau. So, on the Bangombé plateau, Mn-contents increase towards the south, whereas the protore thickness increases towards the NNE. Moreover sand injectites decrease Mn-content in the eastern part of the Bangombé plateau and impact on the economic evaluation of the Mn-carbonates. Currently, the protore is structured by post-sedimentary faults, which lead to a non-continuity of the high Mn levels on the Bangombé plateau.
Le Bassin de Franceville situé au SE du Gabon présente une série de black shales (Formation FB) d'âge Paléoprotérozoïque (2,1 Ga) surmontant les grès de la Formation FA. Ce bassin peu déformé et non métamorphique représente une archive exceptionnelle des processus de dépôt de cette période de l’histoire de la Terre où la vie commence à se développer. En particulier, la Formation FB contient le protore d'un gisement mondial d'oxydes de manganèse exploité par la société Eramet-Comilog. L’objectif de ce travail est de préciser les conditions de formation de ce protore et de le replacer dans l’histoire du remplissage du bassin. Ce protore d'une épaisseur moyenne de 75 m est constitué de carbonates de manganèse ; il a fait l'objet d'une récente campagne de 24 forages carottés d'une profondeur moyenne de 125 m sur le plateau de Bangombé.A travers une approche pluridisciplinaire comprenant l'étude de ces forages et des affleurements clefs du bassin, ce travail porte sur la caractérisation i) de l'environnement de dépôt du protore et des séries qui l'encadrent (du toit du FA au toit du FB) ; ii) du mode de formation des carbonates de Mn à 2,1 Ga et iii) de l'architecture et de la répartition des hautes teneurs en Mn du protore qui représente un gisement potentiel du futur.L’étude pétro-sédimentaire détaillée a permis de distinguer neuf unités (U1 à U9) au sein de la Formation FB organisées suivant un cycle rétrogradant jusqu’à U5 puis progradant jusqu’à U9. Ce découpage montre une évolution du milieu de dépôt depuis un domaine de shoreface contrôlé par des courants deltaïques (U1) évoluant vers des dépôts d’offshore restreint (U2). Ce bassin enregistre ensuite un système de chenaux-levées turbiditiques (U3) qui alimentent un réseau d'injectites reconnu sur l’ensemble du Pl. de Bangombé et qui traverse 150 m de série (U4 à U7) en affectant le protore et ainsi les teneurs en Mn. L'environnement de dépôt du protore (U5 et U6) marque l’isolement du bassin qui devient affamé et contrôlé par une sédimentation biochimique à l’origine du dépôt des carbonates de Mn. L'Unité 7 correspond à la réouverture des apports détritiques en domaine d'offshore supérieur puis en domaine de shoreface dominé par des dépôts de tempêtes et de chenaux sous-aquatiques deltaïques (U8), et enfin lagunaire (U9) dans lequel apparaissent les premiers métazoaires de l’histoire de la planète, suivant une séquence régressive.Une étude géochimique a permis de préciser les conditions de dépôt du protore qui se forme en milieu alcalin anoxique à sub-oxique. Dans ce milieu, nous montrons pour la première fois une précipitation directe des carbonates de Mn sous forme bactériomorphe induite par l'activité photosynthétique des cyanobactéries qui consomment le CO2/HCO3 et conduisent à une augmentation du pH favorable à la formation des carbonates de Mn. L'activité cyanobactérienne est conditionnée par l’absence de courants de fond qui augmentent la turbidité du milieu et stoppent cette dernière.Les corrélations diagraphiques et séquentielles permettent de préciser la répartition spatiale et temporelle du FB permettant ainsi de replacer le protore dans l’histoire tectono-sédimentaire du bassin. Une première phase syn-tectonique (U1 à U3) contrôle l’épaisseur et la mise en place de dépôts turbiditiques dans les parties subsidentes, de dépôts argileux sur les pentes et de dépôt de carbonates sur les hauts-fonds. La seconde phase post tectonique (U4 à U7) permet la mise en place de dépôts relativement isopaques, bien que le protore enregistre une subsidence plus importante au nord du Pl. de Bangombé. On observe ainsi, sur le Plateau de Bangombé, des teneurs en Mn qui augmentent vers le sud alors que l’épaisseur du protore augmente vers le NNE. Postérieurement au dépôt du FB, le protore est structuré par des failles qui le compartimentent en touches de piano limitant ainsi sa continuité sur le Plateau de Bangombé.
https://hal.archives-ouvertes.fr/tel-01621460

tel-01621460
https://hal.archives-ouvertes.fr/tel-01621460
https://hal.archives-ouvertes.fr/tel-01621460/document
https://hal.archives-ouvertes.fr/tel-01621460/file/these_Dubois2017-MnGabon.pdf

Éditeur(s) : HAL CCSD
Résumé : In a perfect-deficit approach (Yi, 2012), the daily maximum carbon storage capacity (CPC) of a given ecosystem for each year defines the perfect annual CPC curve. Deficits are the differences in the daily observational data for a given year against a perfect curve. The area between this curve and instantaneous canopy photosynthetic rates represents the potential productivity. Using an 11-year (2004 – 2014) eddy covariance flux and meteorological data, this perfect-deficit approach was used to examine the relationship between potential productivity and droughts occurring in 2005 and 2010 in a tropical rainforest of French Guiana, South America. Surprisingly, CPC deficits were only reduced by 24% (2005) and 19% (2010) from their respective perfect CPCs, indicating a subtle effect of drought to ecosystem productivity. Highest precipitation occurred in 2010 but precipitation deficits dropped drastically during this year (71% reduction from its perfect value) which reflects a drought condition. However, its deficits showed no correlation annually and seasonally. Soil water content (SWC) appeared to be the single driver for CPC deficits during long dry periods but is weakly correlated (r = 0.30; P <0.01 and r = 0.31; P <0.01, in 2005 and 2010, respectively). These results indicate that soil water is not a major limiting factor for productivity of this ecosystem during drought periods. In contrast, global radiation (Rg) corresponds to the peak of CPC deficits in 2010, but only 19% had been reduced from its ideal value. Yet, highest gross primary production (GPP) of 4106±231 gCm−2yr−1 occurred this year (mean 3753±231 gCm−2yr−1). Therefore, smaller deficits in Rg coupled with sufficient water may have induced higher productivity in 2010. Nevertheless, weaker correlations between potential productivity and climatic drivers may imply that other controlling aspects such as biological constraints may also have an effect to the dynamics of potential productivity during drought events, hence, must also be considered.
AGU Fall Meeting 2015
San Francisco, United States

hal-01269439
https://hal.archives-ouvertes.fr/hal-01269439
PRODINRA : 338570

Éditeur(s) : Elsevier Science Bv
Résumé : Fluid escape structures on the Nile Deep Sea Fan were investigated during the MEDIFLUX MIMES expedition in 2004. Mud volcanoes, pockmarks and authigenic carbonate structures were surveyed for the first time with a high-resolution deep-towed 75 kHz sidescan sonar and a 2-8 kHz Chirp sediment echosounder. In combination with existing multibeam bathymetry and detailed seafloor in situ geological observations, these new data allowed detailed seep analyses. About 60 gas flares were detected acoustically in the water column from the sidescan sonar raw data at water depths from 770 to 1700 m. These gas flares coincide at the seabed with 1) the centres of the mud volcanoes where mud is also extruded, 2) the borders of the mud volcanoes where the emitted gases contribute to the precipitation of authigenic carbonates, and 3) to the edges of broad sheets of authigenic carbonates. Subsurface sediments are commonly disturbed by ascending fluids throughout the delta, with an abundance of seep-related carbonate structures on the seafloor. The feeder channels below mud volcanoes, similar to the gas conduits below the widespread carbonate crust structures and pockmarks, are relatively narrow and, for the vast majority of them, do not exceed a few metres in diameter. The seeps on the Nile Deep Sea Fan clearly follow lineations on the seafloor that we can relate to faults. (C) 2010 Elsevier B.V. All rights reserved.
Marine Geology (0025-3227) (Elsevier Science Bv), 2010-09 , Vol. 275 , N. 1-4 , P. 1-19

Droits : 2010 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/00013/12457/9766.pdf
DOI:10.1016/j.margeo.2010.04.003
http://archimer.ifremer.fr/doc/00013/12457/

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 European Geosciences Union
Résumé : International audience
The seasonal climate drivers of the carbon cycle in tropical forests remain poorly known, although these forests account for more carbon assimilation and storage than any other terrestrial ecosystem. Based on a unique combination of seasonal pan-tropical data sets from 89 experimental sites (68 include aboveground wood productivity measurements and 35 litter productivity measurements), their associated canopy photosynthetic capacity (enhanced vegetation index, EVI) and climate, we ask how carbon assimilation and aboveground allocation are related to climate seasonality in tropical forests and how they interact in the seasonal carbon cycle. We found that canopy photosynthetic capacity seasonality responds positively to precipitation when rainfall is < 2000 mm yr(-1) (water-limited forests) and to radiation otherwise (light-limited forests). On the other hand, independent of climate limitations, wood productivity and litterfall are driven by seasonal variation in precipitation and evapotranspiration, respectively. Consequently, light-limited forests present an asynchronism between canopy photosynthetic capacity and wood productivity. First-order control by precipitation likely indicates a decrease in tropical forest productivity in a drier climate in water-limited forest, and in current light-limited forest with future rainfall < 2000 mm yr(-1).
ISSN: 1726-4170

hal-01557759
https://hal.univ-lorraine.fr/hal-01557759
https://hal.univ-lorraine.fr/hal-01557759/document
https://hal.univ-lorraine.fr/hal-01557759/file/bg-13-2537-2016.pdf
DOI : 10.5194/bg-13-2537-2016

Éditeur(s) : Elsevier
Résumé : We report on a multidisciplinary study of cold seeps explored in the Central Nile deep-sea fan of the Egyptian margin. Our approach combines in situ seafloor observation, geophysics, sedimentological data, measurement of bottom-water methane anomalies, pore-water and sediment geochemistry, and Th-230/U dating of authigenic carbonates. Two areas were investigated, which correspond to different sedimentary provinces. The lower slope, at similar to 2100 m water depth, indicates deformation of sediments by gravitational processes, exhibiting slope-parallel elongated ridges and seafloor depressions. In contrast, the middle slope, at similar to 1650 m water depth, exhibits a series of debris-flow deposits not remobilized by post-depositional gravity processes. Significant differences exist between fluid-escape structures from the two studied areas. At the lower slope, methane anomalies were detected in bottom-waters above the depressions, whereas the adjacent ridges show a frequent coverage of fractured carbonate pavements associated with chemosynthetic vent communities. Carbonate U/Th age dates (similar to 8 kyr BP), pore-water sulphate and solid phase sediment data suggest that seepage activity at those carbonate ridges has decreased over the recent past. In contrast, large (similar to 1 km(2)) carbonate-paved areas were discovered in the middle slope, with U/Th isotope evidence for ongoing carbonate precipitation during the Late Holocene (since similar to 5 kyr BP at least). Our results suggest that fluid venting is closely related to sediment deformation in the Central Nile margin. It is proposed that slope instability leads to focused fluid flow in the lower slope and exposure of 'fossil' carbonate ridges, whereas pervasive diffuse flow prevails at the unfailed middle slope.
Marine Geology (0025-3227) (Elsevier), 2009-06 , Vol. 261 , N. 1-4 , P. 92-104

Droits : 2009 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/2009/publication-6586.pdf
DOI:10.1016/j.margeo.2008.10.008
http://archimer.ifremer.fr/doc/00000/6586/

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
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 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 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
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 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 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
Résumé : Eight drill cores cutting through the Mn-carbonate bearing black shales from the Bangombé Plateau were studied. Mn-carbonates (up to 80 m thick) are underlain by laminated pyrite rich shales with organic carbon contents of about 4 wt. % and MnO contents of about 6 wt. %. Mn and Fe, S poor shales are intercalated. Mn-carbonate rich shales (20-29 wt. % MnO) have low contents of phyllosilicates, but are rich in organic carbon (about 7 wt. %) with moderate S contents (about 2 wt. %). All shale facies were deposited in a closed basin through suspension settling and precipitations under anoxic conditions. The Mn-carbonates, towards the top, were formed most likely under suboxic conditions. Pyrite and Mn-carbonates are characterized by bacteriomorphous structures. The latter are composed of micrometric carbonates finely intergrown with clays, quartz and organic matter. They formed around and corroded the dolomite and/or organic matter. Mn-carbonates and pyrite both form also several tenths of micrometer large agglomerates and sub-automorphous grains. The agglomerates can be attributed to evolving diagenesis. Carbonate chemistry varies mainly from rhodochrosite to dolomite. The present results point to primary microbial Mn-carbonate formation. No signs for a Mn-oxide precursor were detected. Slumping and shearing structures, distortion and disruption of thin pyrite beds indicate synsedimentary deformations.
13th Biennial SGA Meeting
Nancy, France

hal-01356155
https://hal.archives-ouvertes.fr/hal-01356155

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
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
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 Public Library of Science
Résumé : Climate models predict a range of changes in tropical forest regions, including increased average temperatures, decreased total precipitation, reduced soil moisture and alterations in seasonal climate variations. These changes are directly related to the increase in anthropogenic greenhouse gas concentrations, primarily CO2. Assessing seasonal forest growth responses to climate is of utmost importance because woody tissues, produced by photosynthesis from atmospheric CO2, water and light, constitute the main component of carbon sequestration in the forest ecosystem. In this paper, we combine intra-annual tree growth measurements from published tree growth data and the corresponding monthly climate data for 25 pan-tropical forest sites. This meta-analysis is designed to find the shared climate drivers of tree growth and their relative importance across pan-tropical forests in order to improve carbon uptake models in a global change context. Tree growth reveals significant intra-annual seasonality at seasonally dry sites or in wet tropical forests. Of the overall variation in tree growth, 28.7% was explained by the site effect, i.e. the tree growth average per site. The best predictive model included four climate variables: precipitation, solar radiation (estimated with extrasolar radiation reaching the atmosphere), temperature amplitude and relative soil water content. This model explained more than 50% of the tree growth variations across tropical forests. Precipitation and solar radiation are the main seasonal drivers of tree growth, causing 19.8% and 16.3% of the tree growth variations. Both have a significant positive association with tree growth. These findings suggest that forest productivity due to tropical tree growth will be reduced in the future if climate extremes, such as droughts, become more frequent.
ISSN: 1932-6203

hal-01268529
https://hal.archives-ouvertes.fr/hal-01268529
https://hal.archives-ouvertes.fr/hal-01268529/document
https://hal.archives-ouvertes.fr/hal-01268529/file/journal.pone.0092337.PDF
DOI : 10.1371/journal.pone.0092337

Éditeur(s) : HAL CCSD E Schweizerbart Science Publishers
Résumé : The occurrence and preservation of aragonite in eclogite-facies rocks of north-eastern Corsica is linked to an uncommon microtexture. Aragonite exclusively occurs as oriented fibres in garnet crystals of a graphitic, more or less siliceous marble that immediately overlies a serpentinite body of the meta-ophiolitic unit. The arrangement of the fibres is grossly radial, but more clearly sectoral in subhedral garnet, the fibres growing perpendicular to the garnet/matrix interface. Raman mapping reveals that the carbonate is calcite in the matrix and in poikiloblastic garnet cores, and that the fibres in the garnet mantle are aragonite alone in the case of a carbonate matrix, and both aragonite and quartz (in distinct fibres) in a quartz–carbonate matrix. These features are interpreted as prograde intergrowths, the result of garnet nucleation and growth in a calcite and then aragonite matrix (±quartz). Upon further heating and/or decompression, the aragonite matrix transformed back to calcite while the carbonates included in garnet retained their original structure, in spite of the relatively high temperature attained (ca. 500 °C). These aragonite relics are one more example of the preservation of a high-pressure polymorph through mechanical shielding of inclusions in a rigid host. The aragonite–garnet intergrowths are similar to quartz–garnet intergrowths described in amphibolite-facies graphitic schists. They are evidence that oriented inclusions in garnet are not necessarily precipitates (‘exsolutions'). Unlike precipitates, their orientation is controlled more by the shape of the garnet growth front than by symmetry constraints.
ISSN: 0935-1221

hal-00411136
https://hal.archives-ouvertes.fr/hal-00411136
DOI : 10.1127/0935-1221/2008/0020-1892

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The present study reports data on CO2-rich geothermal waters and their associated carbonate deposits from the SW part of the Permian Lodève Basin (South of France). Both waters and carbonates are enriched in 226Ra, with activities up to 2.2 Bq/L and 3.5 Bq/g respectively. A series of carbonate samples precipitated around the studied wells since 1990 were dated through the 226Ra-210Pb and 228Ra-228Th methods, and the results are discussed in a new Concordia diagram. While both methods give comparable dates for many samples, Ra-Pb ages are sometimes much older than Ra-Th ages. We propose that these discrepancies result from the adsorption of 222Rn daughter nuclides in such a Rn-rich environment. The (228Ra/226Ra)0 activity ratios calculated at the time of deposition are remarkably constant for about 12 years, suggesting the presence of a steady-state aquifer. The low (228Ra/226Ra)0 ratios (0.348 ± 0.008) are best explained if most of the Ra derives from the Cambrian carbonate series (mainly dolostone) underlying the Permian Basin, which have low Th/U and similar (228Ra/226Ra) ratios. This study suggests that Ra and other alkaline-earth elements do not necessarily originate from the rocks surrounding the deep geothermal reservoir, but rather may be introduced into the CO2-rich water during its transfer towards the surface and interaction with carbonate rocks.
ISSN: 0009-2541

hal-01053715
https://hal.archives-ouvertes.fr/hal-01053715
DOI : 10.1016/j.chemgeo.2014.02.008