Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A reactive percolation experiment was conducted by injecting seawater into a permeable olivine aggregate at 190 °C and 19 MPa to explore the relationships between hydration reactions and hydrodynamic properties during the onset of serpentinization in the ultramafic lithosphere exposed at mid-ocean ridges. The experiment was stopped after 23 days when the sample became impermeable. The initial flow rate was 0.2 mL/h and then was decreased down to 0.06 mL/h after 8 days. Permeability decreased continuously throughout the experiment. The analyses of fluid chemistry time series and of the mineralogy and structure of the reacted sample showed olivine dissolution and precipitation of proto-serpentine, brucite and Fe-oxides. These reactions are controlled by coupled hydrodynamic and chemical processes interacting at different time and spatial scales. Their first characteristic is the production of silica rich outlet fluids in disequilibrium with the observed reacted mineral assemblages. These compositions are interpreted as resulting from a suite of coupled dissolution-precipitation reactions, controlled at the pore scale by surface kinetic processes, that rapidly reaches steady-state (constant fluid composition independent of fluid flux). Hence, the effective rate of serpentinization was controlled, to the first order, by the transport of reactants during the experiment. Mass balance calculations show that the rate of olivine conversion was fast (0.2-0.5 wt%/day), yet only ∼8 wt% of the olivine sample reacted, because the permeability drop limited fluid circulation. Porosity varied little during the experiment compared to permeability changes: the decrease of permeability was explained by the structure of the newly formed serpentine favouring the clogging of fluid paths. The rate at which permeability decreased was the fastest at low flux conditions. This suggests that permeability changes were not controlled simply by the kinetics of the serpentinization reactions, but mainly reflected the development of low Peclet pore scale zones forming micro-environments that control the serpentinization reaction-paths. These results outline the need to take into account the coupling of hydrodynamic and chemical processes when modelling the effects of reactive transport within the hydrating oceanic lithosphere.
ISSN: 0012-821X

hal-00855043
https://hal.archives-ouvertes.fr/hal-00855043
DOI : 10.1016/j.epsl.2013.03.052

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Coastal aquifers often display seawater intrusion resulting in the formation of a salty water wedge progressing inland. This study investigates the mass transfers in the mixing zone at the freshwater-seawater interface where the water is out of equilibrium with the rock-forming carbonates. Investigations were conducted in two boreholes, separated by 5 m, at the Ses Sitjoles test site (Mallorca Island, Spain) where repeated electrical conductivity logs of the formation and the saturating fluid, as well as regular pore-water sampling and permanent downhole multi-parameter monitoring of the water were performed over a period of 9 a. In the mixing zone, the significant acidification, the calcite saturation index profile and the Ca concentration profile cannot be explained by conservative mixing nor by dissolution-precipitation reactions only. Conversely, the analysis of organic C content and of the distinctly different time-resolved pH profiles measured in the two boreholes suggests the development of perennial biomass that triggers calcite dissolution. Moreover, the presence of biomass seems to be correlated with the permeability and vertical connectivity at the meter-scale. It is speculated that the mechanism could be self-activated because the microbiological activity induces calcite dissolution and tends to increase porosity and permeability that favors biomass development.
ISSN: 0883-2927

hal-00937665
https://hal.archives-ouvertes.fr/hal-00937665
DOI : 10.1016/j.apgeochem.2013.09.011

Éditeur(s) : Gauthier-Villars
Résumé : An experimental techniques to estimate the influence of dissolved organic matter (DOM) on remote sensing of chlorophyll in water has been developed, based on the relationship between fluorescence and absorption of light by a substance. The profiles of fluorescence, chlorophyll content in sea water and estimates of light attenuation in water samples were used in the paper. These data have permitted to calculate the regressions linking fluorescence and light absorption at 450 nm by chlorophyll (ABC450) and by DOM (ABD450). The remote sensing needs no correction for DOM if M450 = 100* (ABC450/ABD450) much greater than 100. This technique has been applied to data collected during the international Skagex field experiment in the straits of Skagerrak and Kattegat in spring and autumn of 1990. It was found that M450 <= 100 everywhere in the subsurface layer. Unfavorable conditions for remote sensing of chlorophyll prevailed in the straits because of the uptake of DOM-rich water from the continent and the accumulation of phytoplankton in deeper layers. These and another processes can increase relative content of colored DOM even in waters of open ocean.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1992 , Vol. 15 , N. 3 , P. 255-259

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00100/21159/18778.pdf
http://archimer.ifremer.fr/doc/00100/21159/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report microstructural evidence for fluid-assisted ductile strain localization in a ≤ 50 m-wide mylonitic–ultramylonitic shear zone in the Ronda Peridotite massif, Southern Spain. Strain localization occurred at relatively low pressure (< 0.8 GPa) and moderate temperature (750–1000 °C). Initial deformation by dislocation creep resulted in formation of mylonites. Focusing of aqueous fluids in the shear zone favored the activation of dissolution–precipitation creep, resulting in further strain localization. This process is recorded by two generations of ultramylonitic bands composed of fine-grained, well-mixed olivine–orthopyroxene aggregates. Microstructural observations in the ultramylonites suggest alternating dissolution and precipitation of olivine and orthopyroxene, which may be explained by local changes in silica molality of the percolating fluid (disequilibrium and mass transfer at scales > mm). In the mylonites, olivine shows a crystal preferred orientation (CPO) coherent with dominant (001)[100] glide, probably due to the presence of interstitial fluids during deformation. In the ultramylonites, olivine CPO is weak to very weak, consistently with a decreasing contribution of dislocation creep to deformation. In contrast, fine-grained orthopyroxene in both mylonites and ultramylonites displays a clear CPO characterized by a [001] maximum normal to the foliation, which is not consistent with dislocation glide in any known slip system for orthopyroxene. We interpret this CPO as formed by oriented crystallization during dissolution–precipitation. In the present study, dissolution–precipitation creep predominates only in small-scale ultramylonite bands due to limited fluid availability and localized dynamic permeability. However, this process may be important in intermediate temperature domains of subduction zones, where it may lead to a feedback between strain localization and fluid transport.
ISSN: 0024-4937

hal-01395122
https://hal.archives-ouvertes.fr/hal-01395122
DOI : 10.1016/j.lithos.2016.07.038

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
A CO2-rich brine core-flood experiment in calcite limestone for conditions representative of underground storage (P = 12 MPa and T = 100°C) was performed in order to explore the dissolution mechanisms arising at moderate CO2 partial pressure (0.3 MPa). An increase of the total porosity (φT) accompanied by a persistent permeability (k) decrease was measured. The mechanisms controlling this atypical anticorrelated k − φT relationship were investigated from the analysis of high-resolution X-ray microtomography images of the sample acquired before and after the experiment. All the evidences converge to the conclusion that the ubiquitous decrease of permeability measured during the 44 h of dissolution is due to the clogging of a fraction of the macroporosity by microporous material triggered by the rearrangement of the detached undissolved particles. This mechanism results in the development of low permeability zones bridging the macroporosity.
ISSN: 0094-8276

hal-00903585
https://hal.archives-ouvertes.fr/hal-00903585
DOI : 10.1002/grl.50595

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

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

Éditeur(s) : Elsevier
Résumé : The distribution, partition and speciation of mercury (Hg) were studied along the redox gradient of an anthropogenically perturbed tropical estuary, the Sinnamary Estuary in French Guiana. This system is a partially mixed estuary characterized by an anoxic freshwater end-member, while the marine end member consists of the Amazon Plume. The set up of an artificial oxygenation system in the anoxic freshwater end-member generates sharp gradients of major chemical species (iron, sulfides, etc.) coupled with intense organic matter (OM) turnover. The coexistence of oxygenated waters and dissolved sulfides in an organic rich environment depicts the Upper Sinnamary Estuary (USE: part of Sinnamary Estuary under the tidal influence but upstream of the salt intrusion) as a potential site for Hg methylation. The concentrations of all mercurial species (HgT) in the unfiltered samples (HgTUNF), in the dissolved (HgTD) and particulate (HgTP) phases of the USE average 11 ± 3, 6 ± 2 and 5 ± 3 (i.e. 600 ± 200 pmol g-1) pmol L-1 respectively. Average concentrations of monomethylmercury (MMHg) in the unfiltered (MMHgUNF), dissolved (MMHgD) and particulate (MMHgP) phases were 3.7 ± 1.0, 2.0 ± 0.9 and 1.8 ± 1.2 (i.e. 220 ± 130 pmol g-1) pmol L-1 respectively. Water oxygenation and sulfides concentrations emerged to play a critical role in controlling MMHg levels. Additionally, iron cycling, acid-base mechanisms, and edoxdependent processes were involved in the MMHg partitioning between phases. Overall, the USE constitutes a biogeochemical reactor that gathers partitioning and methylation processes. Thepermanent MMHg inputs from the anoxic freshwater end-member combined with the intense endogenous Hg methylation ensures high MMHg levels in both dissolved and particulate phases. To illustrate, the USE exports 60 ± 20 % more MMHgUNF than it imports: 5.5 ± 0.7 vs. 3.5 ± 1.2 kg y-1.
Geochimica et Cosmochimica Acta (0016-7037) (Elsevier), 2008-07 , Vol. 72 , N. 22 , P. 5416-5430

Droits : 2008 Elsevier Ltd. All rights reserved
http://archimer.ifremer.fr/doc/2008/publication-4223.pdf
DOI:10.1016/j.gca.2008.08.021
http://archimer.ifremer.fr/doc/00000/4223/

Éditeur(s) : Elsevier
Résumé : The distribution and speciation of mercury (Hg) in the water column, the inputs (wet deposition and tributaries) and the outputs (atmospheric evasion and outlet) of an artificial partially anoxic tropical lake (Petit-Sa-Lit reservoir, French Guiana) were investigated oil a seasonal basis in order to appraise the cycling and transformations of this metal. The total mercury (HgT) concentrations in the oxygenated epilimnetic waters averaged 5 +/- 3 pmol L-1 in the unfiltered samples (HgTUNF) and 4 +/- 2 pmol L-1 in the dissolved (HgTD) phase (< 0.45 mu m). On average, the monomethylmercury (MMHg) constituted 8%, 40%, and 18% of the HgT in the dissolved phase, tile particulate suspended matter and in tile unfiltered samples, respectively. Covariant elevated concentrations of particulate MMHg and chlorophyll a in the epilimnion suggest that phytoplankton is ail active component for the MMHg transfer in tile lake. In the anoxic hypolimnion the HgTUNF averages 13 +/- 6 pmol L-1 and tile HgTD 8 +/- 4 pmol L-1. The averages of MMHgP and MMHgD in hypolimnetic waters were two and three times the corresponding values of the epilimnion, 170 +/- 90 pmol g(-1) and 0.9 +/- 0.5 pmol L-1, respectively. In the long dry and wet seasons, at the flooded forest and upstream dam sampling stations, the vertical profiles of MMHgD concentrations accounted for two distinct maxima: one just below the oxycline and the other near the benthic interface. Direct wet atmospheric deposition accounted for 14 moles yr(-1) HgTUNF, with 0.7 moles yr(-1) as MMHgUNF, while circa 76 moles yr(-1) of HgTUNF, with 4.7 moles yr(-1) as MMHgUNF, coming from tributaries. Circa 78 moles (similar to 17% as MMHg) are annually exported through tile dam, while 23 moles yr(-1) of Hg-0 evolve in the atmosphere. A mass balance calculation suggests that the endogenic production of MMHgUNF attained 8.1 moles yr(-1), corresponding to a methylation rate of 0.06% d(-1). As a result, tile Petit-Saut reservoir is a large man-made reactor that has extensively altered mercury speciation in favor of methylated species.
Applied Geochemistry (0883-2927) (Elsevier), 2008-05 , Vol. 23 , N. 5 , P. 1101-1126

Droits : 2008 Elsevier Ltd All rights reserved.
http://archimer.ifremer.fr/doc/2008/publication-4198.pdf
DOI:10.1016/j.apgeochem.2007.11.006
http://archimer.ifremer.fr/doc/00000/4198/

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) : Gauthier-Villars
Résumé : The dissolved Mn distribution on an oceanographic section along 50-degrees-W in the western North Atlantic shows decreasing concentrations in the offshore direction in the surface layer and with depth at the deep water stations. Leachable particulate Mn concentrations are low in the open ocean surface waters and elevated at intermediate depths. Dissolved Al concentrations in the surface layer are higher in the open ocean than on the shelf and the vertical distributions are characterized by surface maxima, a subsurface minimum at almost-equal-to 1 000 m and increasing concentrations in the deep waters. Leachable particulate Al concentrations are elevated on the shelf and in open ocean surface waters compared to the intermediate and deep waters. The Deep Western Boundary Current has high levels of dissolved Al and leachable particulate Mn and Al, and low levels of dissolved Mn. The distribution of dissolved Al is controlled primarily by inputs from atmospheric dust and removal onto biogenic particles. Both fluvial and atmospheric inputs affect dissolved Mn levels with removal occurring primarily by oxidation of Mn2+. The Al distribution is characterized by short residence times in shelf and surface waters and relatively constant distribution coefficients. The Mn distribution is characterized by longer surface water residence times, shorter deep water residence times, and more widely varying distribution coefficients than Al. Removal of Al by a surface adsorption mechanism and Mn by slower oxidation of Mn2+ are consistent with these observations. A model of Mn oxidation kinetics accurately predicts the intermediate depth leachable particulate Mn maximum.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1992 , Vol. 15 , N. 6 , P. 609-619

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00101/21186/18803.pdf
http://archimer.ifremer.fr/doc/00101/21186/

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) : Gauthier-Villars
Résumé : We report here our findings on the chemistry of methane, manganese and chloride dissolved in the interstitial water of the Barbados accretionary complex. The decollement separating the subduction plate from the accretionary wedge is geochemically characterized by high methane and manganese and low chloride concentrations relative to buried seawater. Sandstone layers occurring below the decollement and the compressive structures recording some of the earliest effects of offscraping are also characterized by similar anomalies. A fluid with the same characteristics is also found six kilometres to the east of the deformation front within the oceanic plate. High manganese concentration and low chlorinity also occur in the pore water of the offscraped sediment packages, but without associated anomalous methane concentrations. These results suggest that: Dewatering processes occur below the decollement in association with thermogenic methane production; Fluid with low chlorinity and high methane concentrations circulates mainly along the decollement, its propagation in the oceanic domain and along the main fracture zones being associated with these detachment surfaces; Diagenetic processes essentially control the dissolved manganese concentration and probably affect the methane content of the interstitial waters; The observations made in this paper illustrate advective processes in the front of an accretionary prism.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1991 , Vol. 14 , N. 1 , P. 33-49

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00101/21262/18873.pdf
http://archimer.ifremer.fr/doc/00101/21262/

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

Résumé : Le fluide chaud produit par les forages de la centrale géothermique de Bouillante (Guadeloupe) est enrichi en espèces dissoutes telles que la silice qui peuvent précipiter sous forme de dépôts solides lors de son refroidissement et gêner fortement la production électrique. L’un des principaux objectifs de ce travail de thèse a donc été d’améliorer l’état des connaissances sur les conditions physiques, chimiques et cinétiques de la précipitation de la silice amorphe à Bouillante. Après une étude des caractéristiques physico-chimiques des fluides et des dépôts associés au champ de Bouillante, des expériences sur la cinétique de précipitation de la silice, sur site, pour une large gamme de température (25 - 90°C) et de pH (4 - 12) ont été menées et analysées en détail.Pour l’ensemble de ces expériences, seule la polymérisation (réversible) de la silice dissoute, sous forme de suspensions colloïdales très stables en solution, a été observée. La modélisation des données expérimentales de cinétique montre que la vitesse de polymérisation de la silice suit une loi d’ordre 2 vis-à-vis de la silice dissoute jusqu’à l’équilibre en accord avec une dimérisation de la silice. Par contre, durant l’étape initiale de la réaction, une loi d’ordre 4 semble mieux adaptée, suggérant des réactions de polymérisation plus complexes avec formation de tétramères. La température a un effet limité sur la cinétique de polymérisation de la silice comparé à l’effet du pH qui est beaucoup plus important. L’énergie d’activation de la réaction globale est de 41 - 54 kJ pour des pH compris entre 5 et 8.La caractérisation de la silice précipitée a mis en évidence des différences notables entre la structure poreuse de la silice solide prélevée sur les installations de surface et celle de la silice colloïdale obtenue par polymérisation lors des expériences de cinétique, ce qui semble indiquer que des mécanismes différents interviennent dans ces deux contextes de précipitation de la silice dissoute.Le deuxième objectif de cette thèse était d’évaluer la possibilité de valoriser la silice extraite de l’eau géothermale de Bouillante dans un procédé de traitement des eaux naturelles par adsorption. Pour cela, les propriétés d’adsorption de la silice géothermale brute et fonctionnalisée par le poly(ethylèneimine) (ou PEI) ont été étudiées pour deux polluants : un colorant, le bleu de méthylène et un métal lourd, le plomb. Les résultats obtenus montrent que la silice brute possède une grande capacité d’adsorption vis-à-vis du bleu de méthylène. En outre, la fonctionnalisation de la silice par le PEI permet d’améliorer sa capacité d’adsorption vis-à-vis du plomb en solution, en accord avec un modèle cinétique du pseudo-second ordre suggérant une chimisorption. Le modèle d’isotherme de Redlich-Peterson est également en très bon accord avec les données expérimentales.
The hot geothermal fluid produced by the geothermal power plant of Bouillante (Guadeloupe) contains various dissolved components such as silica that can precipitate as solid deposits during their cooling and cause serious problems on the electricity generation. One of the aim of this study is to improve the understanding on the physical, chemical and kinetics conditions of the amorphous silica precipitation in the Bouillante geothermal field. After a study on the physical and chemical characteristics of the Bouillante fluids and deposits which can form during their exploitation, experiments on the kinetics of silica precipitation, on site, under a large range of temperature (25 – 90°C) and pH (4 – 12) have been carried out and analyzed in detail.During on site kinetics experimentations only dissolved silica polymerization (reversible) as colloidal gel, very stable in solution, was observed. Modeling of the experimental data showed that the kinetics polymerization is characterized by a 2-order kinetic law relative to dissolved silica until the equilibrium that is consistent with silica dimerization. On the other side, the initial stage of the reaction is better characterized by a 4-order kinetic law that suggested more complex polymerization reactions with tetramers formation.Temperature has a little effect on the polymerization kinetics compared with the pH which has an effect more important. The activation energy of silica precipitation calculated between 25 and 90°C, is about 41 - 54 kJ for pH ranging to 5 - 8.The characterization of the silica precipitate reveals significant differences in the porous structure of the silica collected on the surface installations and the one obtained from kinetic experiments that suggests different precipitation mechanisms. The second objective of this thesis was to evaluate the possibility to promote geothermal silica for the treatment of natural waters containing contaminants by adsorption. Adsorption properties of the untreated and functionalized by poly(ethylèneimine) (ou PEI) geothermal silica have been investigated for two pollutants: a colorant, the methylene blue and a heavy metal, the lead.Results showed that untreated silica has a great adsorption capacity concerning the methylene blue. Besides, silica functionalization by the PEI allows improving the adsorption capacity for lead in solution. The adsorption kinetics curves followed a pseudo-second order model consistent with a chimisorption. The isotherm model of Redlich-Peterson fitted well the experimental data.

http://www.theses.fr/2014AGUY0698/document

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 Ocean Drilling Programm
Résumé : This paper provides a summary of postcruise scientific results from Ocean Drilling Program (ODP) Leg 209 available to date, building upon shipboard observations and syntheses summarized in the Leg 209 Initial Results volume. During Leg 209, 19 holes were drilled at 8 sites along the Mid-Atlantic Ridge from 14°43´ to 15°44´N, mainly in residual mantle peridotite intruded by gabbroic rocks, in order to understand the tectonic and structural processes responsible for formation of oceanic lithosphere with abundant residual peridotite exposed on the seafloor coupled with a relatively low proportion of volcanic rocks. Based on proportions of recovered lithologies, the entire area may be underlain by mantle peridotite with ~20%–40% gabbroic intrusions and impregnations. Impregnated peridotites with olivine + two pyroxenes + plagioclase + spinel that apparently formed in equilibrium probably record crystallization from primitive mid-ocean-ridge basalt at pressures of 0.5–0.6 GPa. Metamorphic equilibria record isobaric cooling to ~1100°C at this pressure. Thus, the conductively cooled thermal boundary layer beneath the Mid-Atlantic Ridge in this region is >15 km thick. Combined crystallization and reaction with residual peridotite formed a series of impregnated peridotites recording increasing Na content at nearly constant Mg#; this process could explain some of the variation in fractionation-corrected Na (e.g., Na = 8.0) observed in mid-ocean-ridge basalts. Clinopyroxene textures and compositions record such impregnation processes, and they are particularly well documented for Site 1274. Other Leg 209 gabbroic rocks formed from extensive crystallization of highly evolved melts, indicating that a substantial proportion of melt entering the thermal boundary layer crystallizes entirely beneath the seafloor, with no volcanic equivalent. Alteration of peridotites occurred over a range of temperatures and is the result of three distinct processes: rock-dominated serpentinization with formation of brucite in olivine-rich lithologies, fluid-dominated serpentinization with formation of magnetite and no brucite, and fluid-dominated talc alteration with addition of SiO2 as well as H2O and oxygen. The latter two processes also exhibit detectable trace element metasomatism that is distinct in its character from the igneous impregnation described in the previous paragraph. Microstructures show that most residual peridotites were not ductilely deformed at temperatures less than ~1200°C. Structural and paleomagnetic data require tectonic rotations of relatively undeformed blocks; some rotations probably exceeded 60° around nearly horizontal axes parallel to the rift axis. Rotations occurred along several generations of high-temperature mylonitic shear zones extending deeper than 15 km depth and numerous faults at lower temperature. Early formed shear zones and faults were passively rotated around later features; such a process could have produced low-angle fault surfaces without slip on low-angle faults. This region provides end-member examples of processes that are common at many or most slow-spreading ridges. Osmium isotope ratios indicate an ancient history of depletion for residual peridotites from the 14°–16°N region along the Mid-Atlantic Ridge. Though depleted Os isotope ratios in peridotite have been reported elsewhere along the global ridge system, the values from this region are among the most depleted. In general, Os isotope ratios from mid-ocean-ridge basalts are systematically more radiogenic than Os isotope ratios from ridge peridotite samples, suggesting a polygenetic heterogeneous source for mid-ocean-ridge basalts. Geochemical studies of zircons from Leg 209 gabbroic rocks and impregnated peridotites, together with other ridge and arc-related zircons, indicate that ridge zircons have systematically lower fractionation-corrected U and Th concentrations compared to arc zircons. This observation provides a tool for interpreting the tectonic provenance of ancient detrital zircons and indicates an arclike provenance for Hadean detrital zircons. Geobiological studies and aerobiological studies were also undertaken during Leg 209. The geobiological work found no measurable microbial enhancement of olivine dissolution rate, possibly because the samples from Leg 209 were sterile. The aerobiological study determined that dust from North Africa, collected from the derrick of the JOIDES Resolution during Leg 209, contains a variety of abundant microorganisms.
Proceedings ODP, scientific results, 209

hal-00407966
https://hal.archives-ouvertes.fr/hal-00407966
DOI : 10.2973/odp.proc.sr.209.001.2007

Éditeur(s) : Springer
Résumé : Batch culture experiments using viral enrichment were conducted to test the response of a coastal bacterial community to autochthonous (i.e., co-existing) or allochthonous riverine viruses. The effects of viral infections on bacterial dynamics and activity were assessed by epifluorescence microscopy and thymidine incorporation, respectively, whereas the effect of viral infection on bacterial community composition was examined by polymerase chain reaction-single strand conformation polymorphism 16S ribosomal RNA fingerprinting. The percentages of high nucleic acid-containing cells, evaluated by flow cytometry, were significantly correlated (r (2) = 0.91, n = 12, p < 0.0001) to bacterial production, making this value a good predictor of active cell dynamics along the study. While confinement and temperature were the two principal experimental factors affecting bacterial community composition and dynamics, respectively, additions of freshwater viruses had significant effects on coastal bacterial communities. Thus, foreign viruses significantly reduced net bacterial population increase as compared to the enrichment treated with inactivated virus. Moreover, freshwater viruses recurrently and specifically affected bacterial community composition, as compared to addition of autochthonous viruses. In most cases, the combined treatment viruses and freshwater dissolved organic matter helped to maintain or even enhance species richness in coastal bacterial communities in agreement to the 'killing the winner' hypothesis. Thus, riverine virus input could potentially influence bacterial community composition of the coastal bay albeit with modest modification of bulk bacterial growth.
Microbial Ecology (0095-3628) (Springer), 2009-02 , Vol. 57 , N. 2 , P. 295-306

Droits : 2009 Springer
http://archimer.ifremer.fr/doc/2009/publication-6636.pdf
DOI:10.1007/s00248-008-9428-1
http://archimer.ifremer.fr/doc/00000/6636/

Éditeur(s) : HAL CCSD
Résumé : In order to minimize CO2 atmospheric concentration, a solution consists in sequestrating CO2 in geological reservoirs. To estimate long term risks, it is necessary to quantify the couplings between reaction processes as well as structural and hydrodynamical modifications. We realised two experimental benches enabling injecting CO2-enriched-brine in conditions corresponding to in situ storage (T < 200 oC and P < 200 bar) and developed
an experimental protocol using X-Ray microtomography and fluid and rock analyses in order to measure the variations of physical and chemical parameters.
The study of carbonated reservoirs near the injection well, allows quantifying different k-phi relationships depending on the dissolution processes and triggered by the local fluid chemical composition and initials conditions. Away from the injection well, we observe carbonate precipitation decreasing the permeability. The study of fracturated caprock samples shows that alternative percolation of CO2-enriched-brine and CO2 gas increases the fracture permeability.
The study of silicated rocks indicates carbonate precipitation in zeolite sandstone and sintered dunite grains. Nevertheless, in zeolite sandstone we also observe the precipitation of clay particles located in the uid pathways which decrease strongly the permeability.
Afin de minimiser la concentration en CO2 dans l'atmosphère une solution consiste à le séquestrer dans les réservoirs géologiques. Pour évaluer les risques à long terme, il est nécessaire de quantifier les couplages entre les processus réactionnels et les modifications structurales et hydrodynamiques. Dans cette optique, nous avons construit deux dispositifs expérimentaux permettant d'injecter des saumures chargées en CO2 dans les conditions de stockage (T < 200 °C et P < 200 bar) et mis en oeuvre un protocole expérimental utilisant la microtomographie RX et l'analyse des roches et des fuides pour quantifier les variations des paramètres physiques et chimiques. Dans le cas des réservoirs carbonatés, on observe, près du puits d'injection, une forte variabilité des relations k-phi en fonction du régime de dissolution contrôlé par la chimie locale du fluide, ainsi que par les conditions initiales. A plus grande distance, on observe des processus de précipitation diminuant fortement la perméabilité. L'étude des roches de couverture fracturées (argilite) a montré qu'une percolation alternée d'une saumure chargée en CO2 et de CO2 gaz augmentait la perméabilité de fracture. Dans le cas des roches silicatées, la précipitation de carbonates est mise en évidence aussi bien dans les grès à zéolites que dans les frittés de dunite de San Carlos. Cependant, dans les grès à zéolites, la précipitation d'une phase argileuse est observée dans les chemins d'écoulement et engendre une forte diminution de la perméabilité.
https://tel.archives-ouvertes.fr/tel-00416408

tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408/document
https://tel.archives-ouvertes.fr/tel-00416408/file/These_Luquot.pdf

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

Éditeur(s) : Copernicus Gesellschaft Mbh
Résumé : The distributions of the bio-essential trace element dissolved cobalt (DCo) and the apparent particulate Co (PCo) are presented along the GEOTRACES-A02 deep section from 64(o) N to 50(o) S in the western Atlantic Ocean (longest section of international GEOTRACES marine environment program). PCo was determined as the difference between total cobalt (TCo, unfiltered samples) and DCo. DCo concentrations ranged from 14.7 pM to 94.3 pM, and PCo concentrations from undetectable values to 18.8 pM. The lowest DCo concentrations were observed in the subtropical domains, and the highest in the low-oxygenated Atlantic Central Waters (ACW), which appears to be the major reservoir of DCo in the western Atlantic. In the Antarctic Bottom Waters, the enrichment in DCo with aging of the water mass can be related to suspension and redissolution of bottom sediments a well as diffusion of DCo from abyssal sediments. Mixing and dilution of deep water masses, rather than scavenging of DCo onto settling particles, generated the meridional decrease of DCo along the southward large-scale circulation in the deep western Atlantic. Furthermore, the apparent scavenged profile of DCo observed in the deep waters likely resulted from the persistence of relatively high concentrations in intermediate waters and low DCo concentrations in underlaying bottom waters. We suggest that the 2010 Icelandic volcanic eruption could have been a source of DCo that could have been transported into the core of the Northeast Atlantic Deep Waters. At intermediate depths, the high concentrations of DCo recorded in the ACW linearly correlated with the apparent utilization of oxygen (AOU), indicating that remineralization of DCo could be significant (representing up to 37% of the DCo present). Furthermore, the preferential remineralization of phosphate (P) compared to Co in these low-oxygenated waters suggests a decoupling between the deep cycles of P and Co. The vertical diffusion of DCo from the ACW appears to be a significant source of DCo into the surface waters of the equatorial domain. Summarizing, the dilution due to mixing processes rather than scavenging of DCo and the above-mentioned remineralization could be the two major pathways controlling the cycling of DCo into the intermediate and deep western Atlantic.
Biogeosciences (1726-4170) (Copernicus Gesellschaft Mbh), 2014 , Vol. 11 , N. 6 , P. 1561-1580

Droits : Author(s) 2014. CC Attribution 3.0 License.
http://archimer.ifremer.fr/doc/00241/35223/33727.pdf
DOI:10.5194/bg-11-1561-2014
http://archimer.ifremer.fr/doc/00241/35223/