Flux hydrothermaux dans le manteau lithosphérique : étude expérimentale du processus de serpentinisation

The hydrothermal alteration of the mantle lithosphere at mid-ocean ridges provides a mechanism for transferring heat and mass between the deep Earth and the overlaying ocean. The mantle lithosphere is constituted by ultramafic rocks, also called Peridotites. They comprise more than 70% of olivine, associated pyroxenes and minor mineral phases. The percolation of seawater into the ultramafic basement produces the alteration of olivine and pyroxenes to serpentine through the so-called serpentinization process and is associated to oxidation and carbonation reactions, the later when CO2 is present. The serpentinization process has special interest on H2 production, CO2 storage, development of life, and the production of economically valuable ore-deposits concentrated at hydrothermal vents. The sustainability and efficiency of the reactions requires penetration and renewal of fluids at the mineral-fluid interface. Oceanic detachment faults and fractures are the highly permeable zones allowing seawater derived fluids to penetrate deeply into the mantle lithosphere. However, the serpentinization process lead to the precipitation of low density minerals that can fill the porous network, clogging flow paths efficiently that may in turn modify the hydrodynamic properties and the reactivity of the reacted rocks.This PhD thesis aims at better understanding the feedback effects of chemical reactions on the hydrodynamic rock properties occurred on highly permeable zones during the earliest stages of alteration of the ultramafic basement. It focuses in particular on the changes in texture and chemical reaction paths of ultramafic rocks by assessing the effects of (i) flow rate and (ii) CO2-rich saline fluids. Two suite of reactive percolation experiments were performed at T=170-190°C and P=25MPa. The first suite of experiments consisted in injecting artificial seawater into porous compressed olivine powder cores over a wide range of constant flow rates. X-Ray µ-tomography of high resolution was acquired before and after the experiment run with high flow rates; in order to evaluate the micro-structural changes of the rock occurred during the serpentinization reaction. The second suite of experiments consisted in injecting CO2-rich saline fluids into peridotite cores mechanically fractured.The results allowed us to differentiate: (1) That, a control of flow infiltration rate at the pore-scale can control the local fluid compositions and the development of different reaction paths at the sample-scale. (2) The development of different reaction paths and textural changes in the rock depends on the concentration of CO2 dissolved in solution. (3) The formation of carbonate minerals (MgCO3) can store CO2 in a form of stable mineral at long-term. (4) A control of the concentration of dissolved CO2(g) and the fracture network can enhance/limit the efficiency of CO2-storage in peridotite fractured reservoirs.These new supporting data suggest a complex control of the structure of the ultramafic rocks in serpentinization process and provides new insights for the potential CO2-storage in peridotite fractured reservoirs.L'altération hydrothermale du manteau lithosphérique dans les dorsales médio-océaniques fournit un mécanisme de transfert de chaleur et de masse entre la terre profonde et l'océan recouvrant. Le manteau lithosphérique est constituée de roches ultramafiques, également appelées péridotites. Ils comprennent plus de 70% d'olivine, de pyroxènes associés et de phases minérales mineures. La percolation de l'eau de mer dans le socle ultramafique produit l'altération de l'olivine et des pyroxènes en serpentine par le processus de serpentinisation et il est associé à des réactions d'oxydation et de carbonatation (lorsque le CO2 est présent dans le fluide). Le processus de serpentinisation présente un intérêt particulier pour la production de H2, le stockage du CO2, le développement de la vie et la production de gisements de minerai économiquement intéressants concentrés dans les fumeroles hydrothermaux. La durabilité et l'efficacité des réactions nécessitent la pénétration et le renouvellement des fluides à l'interface fluide-minéral. Les failles et les fractures des détachements océaniques sont les zones hautement perméables qui permettent à l'eau de mer de pénétrer profondément dans le manteau lithosphérique. Cependant, le processus de serpentinisation conduit à la précipitation de minéraux de faible densité qui peuvent remplir le réseau poreux, colmatant les chemins d'écoulement qui peuvent modifier les propriétés hydrodynamiques et la réactivité des roches réagi.Ces travaux de thèse visent à améliorer la compréhension des effets en retour des réactions sur les propriétés hydrodynamique du milieu dans les zones hautement perméables au cours des premières étapes de l'altération du socle ultramafique. Il se concentre en particulier sur les changements de texture et les réactions chimiques des roches ultramafiques en évaluant les effets du (i) débit et (ii) des fluides salins riches en CO2. Deux séries d'expériences de percolation réactive ont été réalisées à T = 170-190°C et P = 25MPa. La première série d'expériences consistait à injecter de l'eau de mer dans des échantillonnes de poudre d'olivine compressé sur une large gamme de débits constants. La tomographie par rayons X de haute résolution a été acquise avant et après l'expérience avec des débits élevés; afin d'évaluer les changements dans la microstructure de la roche lors de la réaction de serpentinisation. La deuxième série d'expériences consistait à injecter des fluides salins riches en CO2 dans des échantillonnes de péridotite fracturés mécaniquement.Les résultats ont permis de différencier: (1) un contrôle du débit du flux à l'échelle du pore peut contrôler la composition du fluide local et le développement de différents chemins de réaction à l'échelle de l'échantillon. (2) Le développement de différentes chemins réactifs et les changements de texture dans la roche dépend de la concentration de CO2 dissous dans la solution. (3) La formation de minéraux carbonatés (MgCO3) peut stocker du CO2 sous forme stable de minéral à long terme. (4) Un contrôle de la concentration de CO2 dissous dans le fluide et du réseau de fractures peut améliorer / limiter l'efficacité du stockage de CO2 dans les réservoirs de péridotite fracturés.Ces nouvelles données suggèrent un contrôle complexe de la structure des roches ultramafiques dans le processus de serpentinisation et fournissent de nouvelles perspectives pour le stockage potentiel du CO2 dans les réservoirs fracturés à la péridotite

Hydrothermal fluxes in the mantle lithosphere : An experimental study of the serpentinization process

L'altération hydrothermale du manteau lithosphérique dans les dorsales médio-océaniques fournit un mécanisme de transfert de chaleur et de masse entre la terre profonde et l'océan recouvrant. Le manteau lithosphérique est constituée de roches ultramafiques, également appelées péridotites. Ils comprennent plus de 70% d'olivine, de pyroxènes associés et de phases minérales mineures. La percolation de l'eau de mer dans le socle ultramafique produit l'altération de l'olivine et des pyroxènes en serpentine par le processus de serpentinisation et il est associé à des réactions d'oxydation et de carbonatation (lorsque le CO2 est présent dans le fluide). Le processus de serpentinisation présente un intérêt particulier pour la production de H2, le stockage du CO2, le développement de la vie et la production de gisements de minerai économiquement intéressants concentrés dans les fumeroles hydrothermaux. La durabilité et l'efficacité des réactions nécessitent la pénétration et le renouvellement des fluides à l'interface fluide-minéral. Les failles et les fractures des détachements océaniques sont les zones hautement perméables qui permettent à l'eau de mer de pénétrer profondément dans le manteau lithosphérique. Cependant, le processus de serpentinisation conduit à la précipitation de minéraux de faible densité qui peuvent remplir le réseau poreux, colmatant les chemins d'écoulement qui peuvent modifier les propriétés hydrodynamiques et la réactivité des roches réagi.Ces travaux de thèse visent à améliorer la compréhension des effets en retour des réactions sur les propriétés hydrodynamique du milieu dans les zones hautement perméables au cours des premières étapes de l'altération du socle ultramafique. Il se concentre en particulier sur les changements de texture et les réactions chimiques des roches ultramafiques en évaluant les effets du (i) débit et (ii) des fluides salins riches en CO2. Deux séries d'expériences de percolation réactive ont été réalisées à T = 170-190°C et P = 25MPa. La première série d'expériences consistait à injecter de l'eau de mer dans des échantillonnes de poudre d'olivine compressé sur une large gamme de débits constants. La tomographie par rayons X de haute résolution a été acquise avant et après l'expérience avec des débits élevés; afin d'évaluer les changements dans la microstructure de la roche lors de la réaction de serpentinisation. La deuxième série d'expériences consistait à injecter des fluides salins riches en CO2 dans des échantillonnes de péridotite fracturés mécaniquement.Les résultats ont permis de différencier: (1) un contrôle du débit du flux à l'échelle du pore peut contrôler la composition du fluide local et le développement de différents chemins de réaction à l'échelle de l'échantillon. (2) Le développement de différentes chemins réactifs et les changements de texture dans la roche dépend de la concentration de CO2 dissous dans la solution. (3) La formation de minéraux carbonatés (MgCO3) peut stocker du CO2 sous forme stable de minéral à long terme. (4) Un contrôle de la concentration de CO2 dissous dans le fluide et du réseau de fractures peut améliorer / limiter l'efficacité du stockage de CO2 dans les réservoirs de péridotite fracturés.Ces nouvelles données suggèrent un contrôle complexe de la structure des roches ultramafiques dans le processus de serpentinisation et fournissent de nouvelles perspectives pour le stockage potentiel du CO2 dans les réservoirs fracturés à la péridotite.The hydrothermal alteration of the mantle lithosphere at mid-ocean ridges provides a mechanism for transferring heat and mass between the deep Earth and the overlaying ocean. The mantle lithosphere is constituted by ultramafic rocks, also called Peridotites. They comprise more than 70% of olivine, associated pyroxenes and minor mineral phases. The percolation of seawater into the ultramafic basement produces the alteration of olivine and pyroxenes to serpentine through the so-called serpentinization process and is associated to oxidation and carbonation reactions, the later when CO2 is present. The serpentinization process has special interest on H2 production, CO2 storage, development of life, and the production of economically valuable ore-deposits concentrated at hydrothermal vents. The sustainability and efficiency of the reactions requires penetration and renewal of fluids at the mineral-fluid interface. Oceanic detachment faults and fractures are the highly permeable zones allowing seawater derived fluids to penetrate deeply into the mantle lithosphere. However, the serpentinization process lead to the precipitation of low density minerals that can fill the porous network, clogging flow paths efficiently that may in turn modify the hydrodynamic properties and the reactivity of the reacted rocks.This PhD thesis aims at better understanding the feedback effects of chemical reactions on the hydrodynamic rock properties occurred on highly permeable zones during the earliest stages of alteration of the ultramafic basement. It focuses in particular on the changes in texture and chemical reaction paths of ultramafic rocks by assessing the effects of (i) flow rate and (ii) CO2-rich saline fluids. Two suite of reactive percolation experiments were performed at T=170-190°C and P=25MPa. The first suite of experiments consisted in injecting artificial seawater into porous compressed olivine powder cores over a wide range of constant flow rates. X-Ray µ-tomography of high resolution was acquired before and after the experiment run with high flow rates; in order to evaluate the micro-structural changes of the rock occurred during the serpentinization reaction. The second suite of experiments consisted in injecting CO2-rich saline fluids into peridotite cores mechanically fractured.The results allowed us to differentiate: (1) That, a control of flow infiltration rate at the pore-scale can control the local fluid compositions and the development of different reaction paths at the sample-scale. (2) The development of different reaction paths and textural changes in the rock depends on the concentration of CO2 dissolved in solution. (3) The formation of carbonate minerals (MgCO3) can store CO2 in a form of stable mineral at long-term. (4) A control of the concentration of dissolved CO2(g) and the fracture network can enhance/limit the efficiency of CO2-storage in peridotite fractured reservoirs.These new supporting data suggest a complex control of the structure of the ultramafic rocks in serpentinization process and provides new insights for the potential CO2-storage in peridotite fractured reservoirs

Experimental study of the effects of solute transport on reaction paths during incipient serpentinization

International audienceThis paper presents the results of 4 reactive percolation experiments set up for investigating the impact of flow rate on serpentinization reaction paths for conditions relevant of the oceanic peridotite sub-seafloor during the initial stages of its hydrothermal alteration. The experiments consisted in injecting artificial seawater into porous compressed olivine powder cores at constant flow rates Q: 0.24, 0.48, 1.14 and 5.21 mL·h−1. The experiments were conducted at constant temperature (170 °C) and pressure (25 MPa) and lasted 11 to 28 days. At the end of the experiments, the outlet fluids composition displayed similar compositions, buffered by the formation of serpentine (aMg2+/a(H+)2 = 9.7–10; aSiO2 = −3.9 to −5.2; pH in situ = 6.1). These values were achieved in a few to up to 300 h for the high flow rate experiment suggesting that they corresponded to a steady-state regime of mass transfer which depended on flow rate. Differences in the composition of fluid versus time and in the structure of reacted samples during and after the four reactive percolation experiments suggested also various incipient serpentinization reaction paths. The low Q experiments produced SiO2(aq) enriched outlet fluids and nodular aggregates were identified covering the reacted olivine surfaces. During high Q experiments, fibrous filaments of proto-serpentine were formed on the olivine surfaces and the fluids progressively achieved steady state compositions similar to the other experiments. These results together with those of previously published reactive percolation experiments lead us to propose two end-member reaction paths for incipient serpentinization of olivine-dominated permeable rocks infiltrated by seawater derived hydrothermal fluids: (1) a transport-controlled reaction path occurring in diffusion dominated zones is characterized by transient brucite precipitation, which produces Mg trapping and Si release in solution, followed by serpentine precipitation and (2) a kinetics-controlled reaction path occurring in advection dominated zones where transport conditions are favorable to Mg leaching and where serpentine precipitates first. The occurrence of these two end-member reaction paths is determined locally by the composition of the fluid, which varies along flow paths. Thus, both reaction paths can coexist in the sample depending on the local pore geometry. Our study shows that the interplay between fluid transport and reaction kinetics controls the chemical fluxes between the mineral surface and the bulk solution, and the incipient serpentinization reaction paths. In natural systems, the scale and distribution of these reaction domains will depend on the complex structure of the ultramafic basement. Our results suggest that the precipitation of serpentine and silica rich phases will be favored in fluid focusing zones such as faults and fractures, whilst formation of brucite will preferentially occur as part of pervasive background serpentinization

The contribution of aqueous catechol-silica complexes to silicification during carbonate diagenesis

Pore-filling and carbonate-replacing silica is exceedingly common in carbonates, but the fundamental geochemical mechanisms that drive these silicification reactions during diagenesis remain poorly understood. An existing mode has proposed that carbonate silicification proceeds through an interface-coupled dissolution-precipitation reaction, but it lacks a mechanism that enables pore fluids to reach the requisite level of supersaturation with respect to silica to allow nucleation and growth. Here, we present a sequence of batch experiments ranging in duration from 7 to 49 days designed to test the hypothesis that these reactions are facilitated by the formation and destruction of organo-silica complexes during diagenesis. Our results illustrate that the stability of organo-silica complexes is dependent upon the concentration of organic molecules in solution, as well as pH, 16 salinity, and solution redox state. Together, these results allow us to present the following scheme for organo-silica complex mediation of silicification reactions: Firstly, the breakdown of organic matter in the presence of siliceous material creates organo-silica complexes, leading to silica-enriched pore fluids, a process which is enhanced by the anoxic conditions accompanying sediment burial. Then, as environmental conditions evolve (fO2, salinity, light, fCO2, pH...), the stability of the organo-silica complexes diminishes, and the organo-silica complexes break down. Simultaneously, the pore fluids become intensely silica-supersaturated in direct proportion to the amount of organic material remaining in solution. The resulting supersaturation drives carbonate silicification via the precipitation of silica minerals, a process which is aided by the presence of silica “nuclei” (such as sponge spicules). This study contributes new data and a conceptual model that will aid in the ongoing quest to understand carbonate silicification reactions and their potential applications in hydrocarbon exploitation and geologic CO2 storage. Moreover, it helps to explain the common association between silica precipitates and organic mineral in the sedimentary rock record

CO2 injection into fractured peridotites: a reactive percolation experiment

International audienceMantle peridotites have the potential to trap CO2 as carbonates. This process observed in ophiolites and in oceanic environments provides a long term and safe storage for CO2. It occurs as a part of a complex suite of fluid–rock reactions involving silicate dissolution and precipitation of hydrous phases, carbonates and minor phases that may in turn modify the hydrodynamic properties and the reactivity of the reacted rocks. The efficiency and lastingness of the process require the renewal of fluids at the mineral-fluid interface. Fractures are dominant flow paths in exhumed mantle sections. This study aims at better understanding the effect of CO2-enriched saline fluids on hydrodynamic and chemical processes through fractured peridotites.Experiments were performed using the reactive percolation bench ICARE Lab 3 – Géosciences Montpellier. It allows monitoring the permeability changes during experiments. Effluents are recurrently sampled for analysing cation concentration, pH and alkalinity. Reacted rock samples were characterized by high resolution X-ray microtomography (ESRF ID19, Grenoble, France) and SEM. Experiments consisted in injecting CO2-enriched brines (NaCl 0.5 M) at a rate of 6 mL.h-1 into artificially fractured cores (9 mm diameter × 20 mm length) of Oman harzburgites at T=170°C and Ptotal = 25 MPa for up to 2 weeks. Fractures are of few µm apertures with rough walls. Three sets of experiments were performed at increasing value of [CO2] (0, 0.1 and 1 mol/kg).All experiments showed a decrease in permeability followed by steady state regime that can be caused by a decrease in the roughness of fracture walls (dissolution dominated process), thus favouring fracture closing, or by the precipitation of secondary phases. Maximum enrichments in Mg, Fe and Ca of the effluent fluids occur during the first 2 hours of the experiments whereas Si displays a maximum enrichment at t = 20 h, suggesting extensive dissolution. Maximum enrichments are observed with the highest values of the [CO2]. After one day, effluent fluid concentrations decrease and become constant. By analysing both the permeability and the outlet fluid concentration one can investigate the coupling processes controlling the transport and the reaction mechanisms that in turn act at maintaining the circulation in the fractures