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

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

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

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

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
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

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study reports petrostructural observations in the pargasite and phlogopite-bearing Finero peridotite massif (Italian Western Alps), which suggest that the pervasive foliation in this massif was formed by deformation concomitant with percolation of hydrous Si-rich melts: (1) diffuse contacts, but systematic parallelism between the pyroxenitic layers and the foliation of the peridotite (2) strong shape and crystal preferred orientations (SPO and CPO), but subhedral or interstitial shapes and weak intracrystalline deformation of the hydrous phases, (3) CPO, but interstitial shapes of the pyroxenes, (4) very coarse olivine grain sizes, which are correlated to the olivine abundance, and (5) elongated shapes, but weak intracrystalline deformation, and extremely weak and highly variable CPO of olivine. The pervasive deformation of the Finero peridotite occurred therefore under conditions that allowed coexistence of H2O–CO2-bearing melts, pargasite, and spinel, that is, temperatures of 980–1080 °C and pressures <2 GPa. The petrostructural observations suggest that the presence of hydrous melts results in accommodation of large amounts of deformation by stress-controlled dissolution–precipitation and advective transport of matter by the melts and in fast grain boundary migration in olivine. By consequence, it produces significant rheological weakening. Water contents in olivine are <4 ppm wt., implying limited contribution of hydration of olivine to weakening. In addition, the analysis of protomylonites composing the external domains of the shear zones that overprint the pervasive foliation indicates that the transition to melt-free conditions results in enhanced contribution of dislocation creep to the deformation. The associated increase of the peridotites' strength leads to onset of strain localization. The latter is not correlated to the local abundance in pargasite or phlogopite, implying that crystallization of amphiboles or phlogopite, even at concentrations of 25 vol.%, does not produce rheological weakening in the upper mantle.
ISSN: 0012-821X

hal-01667879
https://hal.archives-ouvertes.fr/hal-01667879
DOI : 10.1016/j.epsl.2017.08.015

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
To test if hydrogen incorporation by ionic diffusion can occur between a volatile-rich kimberlitic liquid and forsterite, results of high-pressure and high-temperature experiments using a piston-cylinder apparatus at 1200–1300 °C and 1 GPa for durations of 1 min, 5 h, and 23 h, are reported here. Kimberlitic liquid in the system CaO-MgO-Al2O3-SiO2-CO2-H2O and synthetic forsterite single crystals were chosen as a first simplification of the complex natural kimberlite composition. Unpolarized Fourier transform infrared spectroscopy was used to quantify the concentrations of OH in the crystallographically oriented forsterite. Scanning electron microscopy, electron backscattered diffraction, electron microprobe analyses, and transmission electron microscopy were performed to identify the run products. After 5 and 23 h, a forsterite overgrowth crystallized with the same orientation as the initial forsterite single crystal. The kimberlitic liquid has crystallized as micrometer-scale euhedral forsterite neocrystals with random crystallographic orientations, as well as a nanoscale aluminous phase and a calcic phase. Despite theoretical water-saturation of the system and long duration, none of the initial forsterite single crystals display signs of hydration such as hydrogen diffusion profile from the border toward the center of the crystal. Most likely, the presence of CO2 in the system has lowered the H2O fugacity to such an extent that there is no significant hydration of the starting forsterite single crystal or its overgrowth. Also, the presence of CO2 enhances rapid forsterite crystal growth. Forsterite growth rate is around 2 × 108 μm3/h at 1250 °C. These experimental results suggest a deep mantle origin of the high OH content found in natural mantle-derived xenoliths transported in kimberlites, as reported from the Kaapvaal craton. In agreement with previous studies, it also points out to the fact that significant hydration must take place in a CO2-poor environment.
ISSN: 0003-004X

hal-01217157
https://hal.archives-ouvertes.fr/hal-01217157
DOI : 10.2138/am-2015-5200

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
Arenal volcano is nearly unique among arc volcanoes with its 42 year long (1968–2010) continuous, small-scale activity erupting compositionally monotonous basaltic andesites that also dominate the entire, ~7000 year long, eruptive history. Only mineral zoning records reveal that basaltic andesites are the result of complex, open-system processes deriving minerals from a variety of crystallization environments and including the episodic injections of basalt. The condition of the mafic input as well as the generation of crystal-rich basaltic andesites of the recent, 1968–2010, and earlier eruptions were addressed by an experimental study at 200 MPa, 900–1,050 °C, oxidizing and fluid-saturated conditions with various fluid compositions [H2O/(H2O + CO2) = 0.3–1]. Phase equilibria were determined using a phenocryst-poor (~3 vol%) Arenal-like basalt (50.5−wt% SiO2) from a nearby scoria cone containing olivine (Fo92), plagioclase (An86), clinopyroxene (Mg# = 82) and magnetite (Xulvö = 0.13). Experimental melts generally reproduce observed compositional trends among Arenal samples. Small differences between experimental melts and natural rocks can be explained by open-system processes. At low pressure (200 MPa), the mineral assemblage as well as the mineral compositions of the natural basalt were reproduced at 1,000 °C and high water activity. The residual melt at these conditions is basaltic andesitic (55 wt% SiO2) with 5 wt% H2O. The evolution to more evolved magmas observed at Arenal occurred under fluid-saturated conditions but variable fluid compositions. At 1,000 °C and 200 MPa, a decrease of water content by approximately 1 wt% induces significant changes of the mineral assemblage from olivine + clinopyroxene + plagioclase (5 wt% H2O in the melt) to clinopyroxene + plagioclase + orthopyroxene (4 wt% H2O in the melt). Both assemblages are observed in crystal-rich basalt (15 vol%) and basaltic andesites. Experimental data indicate that the lack of orthopyroxene and the presence of amphibole, also observed in basaltic andesitic tephra units, is due to crystallization at nearly water-saturated conditions and temperatures lower than 950 °C. The enigmatic two compositional groups previously known as low- and high-Al2O3 samples at Arenal volcano may be explained by low- and high-pressure crystallization, respectively. Using high-Al as signal of deeper crystallization, first magmas of the 1968–2010 eruption evolved deep in the crust and ascent was relatively fast leaving little time for significant compositional overprint by shallower level crystallization.
ISSN: 0010-7999

hal-01115717
https://hal.archives-ouvertes.fr/hal-01115717
DOI : 10.1007/s00410-014-1040-4

Éditeur(s) : HAL CCSD
Résumé : This study provides additional constraints on the relations between deformation, hydration and percolation of fluids and melts in the subcontinental lithospheric mantle beneath a craton and a rift, as well as their implication on its geodynamical behaviour. I have analysed the microstructures, the CPOs, and the hydrogen content of mantle xenoliths from the Kaapvaal craton, and two sets of xenoliths from different localities along the East African Rift (North Tanzanian Divergence and SE Ethiopia).The coarse-granular microstructures and the well-defined CPOs in Kaapvaal peridotites suggest a deformation followed by a long quiescence time. Orthorhombic olivine CPOs predominates, but axial-[100] and axial-[010] are also measured. Cratonic peridotites record multiple metasomatic episodes, leading to a significant compositional heterogeneity, which cannot be imaged by seismic studies. Olivine hydrogen contents are variable, but tend to increase until 150 km depth, reaching up to 50 ppm wt. H2O. The deeper samples are almost dry. Piston-cylinder experiments on hydrogen diffusion between a volatile-rich kimberlitic melt and forsterite suggest that the presence of CO2 in the system could significantly decrease water fugacity and thus forsterite hydration. These experimental results indicate that the hydrogen contents measured in olivine were acquired during a metasomatic event rather than during xenolith extraction by kimberlites. However, this metasomatism was not followed by remobilization of the cratonic root.In the North Tanzanian Divergence, localities within the rift axis and the volcanic transverse belt (Lashaine and Olmani) show significant differences in microstructures and olivine CPO patterns. In Lashaine, coarse-granular microstructures and orthorhombic to axial-[100] CPO patterns in olivine can be explained by transpressional deformation during the formation of the Mozambique belt, or by the occurrence of a remnant of a cratonic domain embedded within the Mozambique belt. Within the rift axis, porphyroclastic to mylonitic microstructures suggest a recent rift-related deformation accompanied by syn-kinematic melt-rock reactions, and followed by variable annealing. The strong heterogeneity in microstructures and olivine CPO suggests that this deformation was acquired during multiple tectonic events probably linked to episodic magma percolation, separated by quiescence episodes. The axial-[100] patterns in olivine and the oblique fast directions reported by SKS studies are coherent with transtensional deformation within the lithospheric mantle beneath the rift.The peridotites from SE Ethiopia are less recrystallized than the rift-axis Tanzanian peridotites, displaying coarse-porphyroclastic microstructures. Microstructures and orthorhombic CPOs in olivine suggest syn- to post-metasomatic deformation. S-waves polarization anisotropies calculated for these samples cannot explain alone the delay times reported by SKS studies in this part of the East-African Rift.
Les travaux réalisés durant cette thèse apportent de nouvelles contraintes sur les relations entre déformation, hydratation et percolation de fluides et/ou de magmas dans le manteau subcontinental sous un craton et sous un rift, et leurs implications sur son comportement rhéologique. Il repose sur l'analyse des microstructures, des OPRs et des teneurs en hydrogène de xénolites mantelliques du craton du Kaapvaal, et sur deux séries de xénolites provenant de différentes localités le long du rift Est-Africain (Divergence Nord Tanzanienne et SE de l'Ethiopie). Les microstructures granulaires à gros grains et les OPRs bien définies des péridotites du craton du Kaapvaal sont cohérentes avec un épisode de déformation suivi d'une longue période de quiescence. Les OPRs de l'olivine sont majoritairement à symétrie orthorhombique, mais des symétries axiale-[100] et axiale-[010] sont aussi mesurées. Les péridotites cratoniques enregistrent de multiples épisodes métasomatiques, ayant entraîné une hétérogénéité de compositions à petite échelle ne pouvant être détectée par les études sismiques. Les teneurs en hydrogène mesurées dans l'olivine sont variables, mais ont tendance à augmenter jusqu'à 150 km de profondeur, atteignant alors jusqu'à 50 ppm wt. H2O. En dessous de cette profondeur, les échantillons montrent des teneurs en hydrogène très faibles. Les expériences réalisées en piston-cylindre sur la diffusion de l'hydrogène issue d'un liquide kimberlitique vers de la forstérite suggèrent que la fugacité en eau pourrait fortement être diminuée par la présence de CO2, empêchant l'hydratation de l'olivine durant extraction des xénolites par les kimberlites. Ces résultats expérimentaux suggèrent que les teneurs en hydrogène dans l'olivine des péridotites du craton du Kaapvaal ont été acquises durant un épisode métasomatique en profondeur et non pendant leur extraction par les kimberlites. Ces teneurs n'ont toutefois pas à ce jour entraîné de remobilisation de la racine cratonique. Enfin, le calcul des propriétés sismiques des péridotites cratoniques révèle que les anisotropies générées par les OPRs de ces échantillons sont suffisantes pour expliquer les anisotropies mesurées par les ondes SKS et les ondes de surface.Les xénolites de la Divergence Nord-Tanzanienne, montrent des variations significatives de microstructures et d'OPR de l'olivine entre les péridotites des localités dans l'axe du rift et celles de la chaîne volcanique transverse (Lashaine et Olmani). A Lashaine, les microstructures granulaires à gros grains et les OPRs de type orthorhombique et axial-[010] peuvent être expliquée par une déformation en transpression liée à la formation de la chaîne Mozambique ou par la présence d'une relique d'un domaine cratonique à l'intérieur de la chaîne Mozambique. Dans l'axe du rift, les microstructures porphyroclastiques à mylonitiques suggèrent une déformation plus récente, accompagnée de réactions magma-roche sous des conditions proches du solidus, suivie d'un recuit variable. L'hétérogénéité des microstructures enregistrées par les échantillons du rift suggère de multiples épisodes de déformation localisée, probablement liés à l'injection percolation épisodique de magmas, espacés de périodes d'accalmie. Les OPRs de l'olivine de type axial-[100] et l'orientation des directions de polarisation des ondes SKS suggère que le rift s'est formé en régime de transtension Les péridotites du Sud-Est de l’Éthiopie présentent des microstructures porphyroclastiques à gros grains moins recristallisées qu'en Tanzanie. Les microstructures et les OPRs principalement de type orthorhombique suggèrent une déformation syn- à post-métasomatisme. Les anisotropies de polarisation des ondes S calculées pour ces échantillons sont insuffisantes pour expliquer à elles seules les déphasages des ondes SKS dans cette partie du rift.
https://tel.archives-ouvertes.fr/tel-01684759

Droits : info:eu-repo/semantics/OpenAccess
NNT : 2014MON20139
tel-01684759
https://tel.archives-ouvertes.fr/tel-01684759
https://tel.archives-ouvertes.fr/tel-01684759/document
https://tel.archives-ouvertes.fr/tel-01684759/file/43443_BAPTISTE_2014_archivage_cor.pdf

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
North Tanzanian Divergence is the first stage of continental break-up of East African Rift (<6 Ma) and is one of the most concentrated areas of carbonatite magmatism on Earth, with singular Oldoinyo Lengai and Kerimasi volcanoes. Hanang volcano is the southernmost volcano in the North Tanzanian Divergence and the earliest stage of rift initiation. Hanang volcano erupted silica-undersaturated alkaline lavas with zoned clinopyroxene, nepheline, andradite-schorlomite, titanite, apatite, and pyrrhotite. Lavas are low MgO-nephelinite with low Mg# and high silica content (Mg# = 22.4–35.2, SiO2 = 44.2–46.7 wt%, respectively), high incompatible element concentrations (e.g. REE, Ba, Sr) and display Nb–Ta fractionation (Nb/Ta = 36–61). Major elements of whole rock are consistent with magmatic differentiation by fractional crystallization from a parental melt with melilititic composition. Although fractional crystallization occurred at 9–12 km and can be considered as an important process leading to nephelinite magma, the complex zonation of cpx (e.g. abrupt change of Mg#, Nb/Ta, and H2O) and trace element patterns of nephelinites recorded magmatic differentiation involving open system with carbonate–silicate immiscibility and primary melilititic melt replenishment. The low water content of clinopyroxene (3–25 ppm wt. H2O) indicates that at least 0.3 wt% H2O was present at depth during carbonate-rich nephelinite crystallization at 340–640 MPa and 1050–1100 °C. Mg-poor nephelinites from Hanang represent an early stage of the evolution path towards carbonatitic magmatism as observed in Oldoinyo Lengai. Paragenesis and geochemistry of Hanang nephelinites require the presence of CO2-rich melilititic liquid in the southern part of North Tanzanian Divergence and carbonate-rich melt percolations after deep partial melting of CO2-rich oxidized mantle source.
ISSN: 0010-7999

hal-01467390
https://hal.archives-ouvertes.fr/hal-01467390
DOI : 10.1007/s00410-016-1273-5

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 : Our method for the simultaneous determination of the four natural Ra isotopes (Ra-226, Ra-228, Ra-224 and Ra-223) in thermal waters involves a separation of Ra on a selective filter (3 M EMPORE (TM) Radium Rad disk), and a single counting using a broad-energy HPGe detector (BE Ge manufactured by CANBERRA (TM)). The calculation of Ra-223 and (228)a activities requires interference and cascade summing corrections. The Ra-226 activities in CO2-rich thermal waters of the Lodeve Basin (South of France) range from 530 to 2240 mBq/l. The low (Ra-228/Ra-226) activity ratios (0.19-0.29) suggest that Ra is mostly derived from the aquifer carbonates. The short-lived Ra-224 and Ra-223 are probably added to the water through recoil or desorption processes from Th-enriched coatings on the fracture walls.
ISSN: 0969-8043

hal-00475587
https://hal.archives-ouvertes.fr/hal-00475587
DOI : 10.1016/j.apradiso.2009.10.056

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study explores the dynamics of porosity and reactive surface area changes during porous limestone dissolution by CO2-rich water. The Sr and Ca concentrations in both the rock and the outlet solution are used to evaluate the reactive surface area changes of the two rock-forming calcites, i.e. micrite grains and sparite crystals, which have different trace element signatures. The geometric surface area measured with X-ray microtomography decreases slightly whereas the reactive surface area increases continuously with increasing porosity from 20.3 to 30.2%. Surprisingly, changes in reactive surface areas are very different between the two calcites. The reactive surface area changes in the micrite are parabolic while the reactive surface area of sparite increases greatly. The numerical model HYTEC is used to model the change in reactive surface areas during the experiment. Different geometrical models are tested. The model based on spherical-grain dissolution and spherical-pore growth fails to reproduce the experimental results, while the sugar-lump model provides reasonable agreement with the experiment.
ISSN: 0009-2541

hal-00445274
https://hal.archives-ouvertes.fr/hal-00445274
DOI : 10.1016/j.chemgeo.2009.01.032