Éditeur(s) : Elsevier
Résumé : Regardless of the degree of closure of a recirculation system, effluents are produced and replacement water is needed, which limits the possibility of locating a seawater production system away from the shoreline. At the Palavas Ifremer station, in the south of France, a High Rate Algal Pond (HRAP) was operated during several years to treat the effluent from a recirculating aquaculture system before reusing it. The effect of the HRAP-treated water on the recirculation system and on the fish was investigated and the optimal algae growing conditions were defined. The experiments were carried out in three rearing systems: one flow through, one recirculating and one recirculating with a HRAP. The water flow rate, temperature, pH and salinity conditions were similar in all systems. The effect of reusing the HRAP-treated water is very limited (1) on the functioning of the recirculation system and (2) on fish performance, but it allows a significant reduction of the dissolved inorganic nitrogen and phosphorus concentration in the rearing water. HRAP treatment reduced metal accumulation in muscle and liver of RAS fish, except for chromium and arsenic. All biomarkers presented no significant difference between systems, except for Superoxide Dismutase (SOD) and EROD, which showed a higher concentration in RAS and in both recirculating system respectively. (c) 2005 Elsevier B.V. All rights reserved.
Aquaculture (0044-8486) (Elsevier), 2006-03 , Vol. 252 , N. 1 , P. 92-101

Droits : 2005 Elsevier
http://archimer.ifremer.fr/doc/2006/publication-2306.pdf
DOI:10.1016/j.aquaculture.2005.11.053
http://archimer.ifremer.fr/doc/00000/2306/

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
Claystone caprocks are often the ultimate seal for CO2 underground storage when residual CO2 gas reaches the reservoir top due to buoyancy. Permeability changes of a fractured claystone due to seepage of CO2-enriched brine and water vapor-saturated CO2 gas are investigated. Results show that brine flow induces a large porosity increase (up to 50%) in the vicinity of the fracture due to dissolution of calcite and quartz, while permeability remains unchanged. Conversely, cyclic flows of CO2-brine and CO2-gas increase the fracture aperture abruptly after each gas flow period, producing a progressive decrease of the caprock seal capacity. Aperture increase is controlled by decohesion of the clay framework within a micrometer-scale-thick layer induced by CO2-gas acidification. Results show that hydraulic aperture increases linearly with duration of the preceding CO2-brine flow period, emphasizing the kinetic control of the quartz grains dissolution during the brine flow periods.
ISSN: 0094-8276

hal-00412332
https://hal.archives-ouvertes.fr/hal-00412332
DOI : 10.1029/2008GL034467

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Numerical programs for simulating flow and reactive transport in porous media is essential for predicting reservoir properties related to CO2 sequestration performance, subsurface storage and risk assessment. In this paper we solve the Navier Stokes' equation using finite difference method, on a simulated porous rock structure, to study the velocity distribution of fluid flowing through it under a constant pressure gradient. A reactive solute carried through the fluid is allowed to interact with the minerals in the rock. This chemical reaction dissolves the mineral which changes the rock structure thus affecting its flow properties. These changes of flow properties are studied with variation in reactive solute concentration and pressure field. The different mechanisms of dissolution responsible for the variation of flow properties for the different parameters is predicted. Before the onset of homogeneous dissolution, variation in porosity follows a power-law behaviour with change in permeability when the latter is scaled by the concentration of the reactive species. The simulation results are compared with available experimental data and found to give a reasonable match.
ISSN: 0022-1694

hal-00757760
https://hal.archives-ouvertes.fr/hal-00757760
DOI : 10.1016/j.jhydrol.2012.05.024

Éditeur(s) : OMICS Publishing Group
Résumé : Coastal tropical shrimp farming may impact the adjacent ecosystems through the release of large quantities of effluents rich in nutrients. In New Caledonia, mangroves are considered as a natural biofilter to reduce impacts on the surrounding World Heritage listed lagoon. Our main objective was to understand the influence of effluent discharge on the biogeochemistry of mangrove sediments. A monitoring of the physico-chemical parameters of mangrove sediments was carried out during a whole year, including active and non active periods of the farm. The parameters studied were: i) benthic primary production (Chl-a concentrations), ii) physico-chemical parameters of sediments (redox potential, pH, salinity, TOC, TN, TS, δ13C and δ15N), iii) concentrations of dissolved nitrogen, iron and phosphorus. A mangrove developing in the same physiographic conditions, presenting the same zonation, and free of anthropogenic input was used as reference. The concentration of benthic Chl-a measured at sediment surface in the effluent receiving mangrove was twice to three times that measured in the control zone whatever the season. We thus suggest that nutrients inputs significantly increased the phytobenthic production in the effluent receiving mangrove during the whole year, even after the cessation of discharges and because of natural seasonal dynamic of phytobenthos. Although the flow of surface OM was increased, the OM content at depth was not higher than in the control mangrove. However, the contribution of mangrove detritus to the sedimentary organic pool was higher probably as a result of higher density and much greater individual size of the mangrove trees. Unlike the control mangrove sediment, the effluent receiving mangrove sediment was not stratified, redox potential values were high and presence of Fe3+ was detected down to 50 cm depth, probably as a result of a larger root system, allowing a better sediment oxygenation and accentuated OM decomposition processes, and thus limiting ecosystem saturation.
Journal of Aquaculture Research & Development (21559546) (OMICS Publishing Group), 2014-07-03 , Vol. 5 , N. 5 , P. 1-13

Droits : 2014 Marchand C, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
http://archimer.ifremer.fr/doc/00251/36253/34801.pdf
DOI:10.4172/2155-9546.1000262
http://archimer.ifremer.fr/doc/00251/36253/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Numerical programs for simulating flow and reactive transport in porous media are essential tools for predicting reservoir properties changes triggered by CO2 underground injection. At reservoir scale, meshed models in which equations are solved assuming that constant macroscopic properties can be defined in each cells, are widely used. However, the parameterization of the dissolution-precipitation problem and of the feedback effects of these processes on the flow field is still challenging. The problem arises from the mismatch between the scales at which averaged parameters are defined in the meshed model and the scale at which chemical reactions occur and modify the pore network geometry. In this paper we investigate the links between the dissolution mechanisms that control the porosity changes and the related changes of the reactive surface area and of the permeability. First, the reactive surface area is computed from X-ray microtomography data obtained before and after a set of dissolution experiments of pure calcite rock samples using distinctly different brine-CO2 mixtures characterizing homogeneous to heterogeneous dissolution regimes. The results are used to validate the power law empirical model relating the reactive surface area to porosity proposed by Luquot and Gauze (2009). Second, we investigate the spatial distribution of the effective hydraulic radius and of the tortuosity, two structural parameters that control permeability, in order to explain the different porosity-permeability relationships observed for heterogeneous and homogeneous dissolution regimes. It is shown that the increase of permeability is due to the decrease of the tortuosity for homogeneous dissolution, whereas it is due to the combination of tortuosity decrease and hydraulic radius increase for heterogeneous dissolution. For the intermediate dissolution regime, identified to be the optimal regime for increasing permeability with small changes in porosity, the increase of permeability results from a large increase in the mean effective hydraulic radius of the sample.
ISSN: 0169-7722

hal-00617671
https://hal.archives-ouvertes.fr/hal-00617671
DOI : 10.1016/j.jconhyd.2010.07.004

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

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

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Most kimberlites contain abundant dunitic nodules. These are centimetre-sized, rounded and multi-grained assemblages of xenocrystic olivine with a wide range of compositions (Fo83 to Fo94). The absence of orthopyroxene and other mantle minerals and the range of olivine compositions have been attributed to reaction between mantle peridotite and (proto)kimberlitic fluid or melt, but the timing of the reaction is a subject of debate. In a kimberlite from the Kangamiut region of Greenland, nodule cores are surrounded by fine-grained outer margins with near-constant Fo contents (∼Fo88) but highly variable minor element contents (e.g. 500–2500 ppm Ni). These margins crystallized from the kimberlite melt and we show that their compositions can be explained by crystallization of olivine alone, if a high partition coefficient for Ni between melt and olivine (DNi > 20) is assumed. Orthopyroxene assimilation is not required, removing the constraint that its dissolution occurred during ascent of the kimberlite magma. Within some nodules, in addition to the usual core-to-margin gradients, we observe asymmetric compositional changes (variable Fo but near-constant minor element contents) across mobile grain boundaries. These changes document fluid percolation at the grain scale that occurred during dynamic recrystallization in the deforming lithospheric mantle. We note that chemical gradients associated with mobile grain boundaries are observed in olivines that cover the entire compositional range of the nodules, and propose that fluid-assisted dynamic recrystallization took place in dunite that was already compositionally heterogeneous. Reaction between peridotite and protokimberlitic melt or fluid and dissolution of orthopyroxene thus occurred within the lithospheric mantle, immediately (a few days) prior to the ascent of the kimberlite melt and the entrainment of the dunite nodules. We propose that the grain boundary zones probably mimic, at a fine scale, the fluid–peridotite interaction that caused, at a larger scale, orthopyroxene dissolution and formation of compositionally diverse olivine in kimberlites.
ISSN: 0022-3530

hal-01277963
https://hal.archives-ouvertes.fr/hal-01277963
DOI : 10.1093/petrology/egv054

Éditeur(s) : Edp Sciences S A
Résumé : A study on nitrogenous and phosphorous waste production in European seabass (Dicentrarchus labrax) was carried out in a flow-through land-based farm. The main objectives were (i) to calculate nitrogenous (N) and phosphorous (P) waste production (particulate and dissolved) from in situ measurements for different rearing ponds with specific fish biomasses, fish sizes and flow rates, (ii) to establish nitrogenous and phosphorous waste production budgets, ratios and equations, and (iii) to compare, for the whole farm, in situ measurements to estimate N and P waste production from waste equations. Waste production was manifest by an increase in concentrations of total ammonia nitrogen, total Kjeldhal nitrogen, particulate nitrogen, dissolved phosphorus and total phosphorus concentrations in the outlet water compared to the inlet water for both batches and whole farm. However, no production of nitrite or nitrate was observed. In our budgets, the N and P amounts from biomass gains and wastes were explained by the N and P derived from feed over the range 83.9-105.2 % and 66.5-104.6 % respectively, depending on the fish batch. Values were respectively 103.4 and 87.5 % for the same calculations in the farm. When the whole-farm waste production was calculated from previous equations derived from batches, and then compared with the measured data, the percentages of recovery (estimated by the ratio predicted data/measured data) were 88 and 94 % for total-N and total-P respectively.
L'étude de la production des déchets (azote et phosphore) d'une ferme de production de bars (Dicentrarchus labrax) est réalisée. Cette étude à pour objectif (i) de mesurer in situ la production des déchets azotés et phosphores sous forme particulaire et soluble, pour différents bassins d'élevage présentant des caractéristiques variables en terme de biomasse de poisson, de taille des poissons, de débit de l'eau de renouvellement, (ii) d'établir des équations de production de déchets à partir des données précédemment acquises, (iii) de comparer, pour l'ensemble des rejets au niveau de la ferme, les résultats obtenus par des mesures in situ, d'une part, et à l'aide des équations, d'autre part. La production de déchets se traduit par une augmentation des concentrations de l'azote particulaire, de l'azote ammoniacal, de l'azote organique dissous, ainsi que du phosphore particulaire et dissous. Aucune augmentation des nitrates et nitrites n'est observée. L'établissement des budgets d'azote et de phosphore permettent de rendre compte, selon les bassins, du devenir de 88,2 à 105,2 % de l'azote et de 66,2 à 104,6 % du phosphore introduits dans les bassins sous forme de nourriture en granulés. L'étude des budgets réalisée par les deux méthodes (mesures in situ et utilisation des équations) montre que les budgets établis à l'aide des équations rendent compte respectivement de 88 et 94 % de récupération de l'azote et du phosphore. Ces résultats sont respectivement de 103,4 et 87,5 % lorsqu'ils sont établis par des mesures in situ.
Aquatic Living Resources (0990-7440) (Edp Sciences S A), 1998-07 , Vol. 11 , N. 4 , P. 247-254

Droits : 1998 Published by Elsevier SAS
http://archimer.ifremer.fr/doc/1998/publication-872.pdf
DOI:10.1016/S0990-7440(98)89007-4
http://archimer.ifremer.fr/doc/00000/872/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
In this paper we solve the Navier Stokes’ equation using finite difference method, on a simulated porous rock structure in 2-D, to study the velocity distribution of fluid flowing through it under a constant pressure gradient. A reactive solute carried through the fluid is allowed to interact with the minerals in the rock. Depending on the rock composition, both dissolution and precipitation reactions may occur. However precipitation occurs only through the cations that are released in the solution due to dissolution. These combined dissolution–precipitation reactions change the porosity, permeability and pore geometry of the sedimentary rock. We study the temporal changes of these properties as functions of Peclet number, concentration of the reactive solute and ratio of Damkholer numbers of dissolution to precipitation. The final flow property is decided by a combination of these parameters.
ISSN: 0022-1694

hal-01115291
https://hal.archives-ouvertes.fr/hal-01115291
DOI : 10.1016/j.jhydrol.2014.10.019

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

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

Éditeur(s) : Elsevier
Résumé : The distribution and speciation of mercury (Hg) in air, rain, and surface waters from the artificial tropical lake of Petit-Saut in French Guiana were investigated during the 2003/04 period. In the air, total gaseous mercury (TGM) at the dam station averaged 12 +/- 2 pmol m(-3) of which > 98% was gaseous elemental mercury (GEM). GEM distribution depicted a day-night cycling with high concentrations (up to 15 pmol m(-3)) at dawn and low concentrations (down to 5 pmol m(-3)) at nightfall. Reactive gaseous mercury (RGM) represented < 1% of the GEM with a mean concentration of 4 3 fmol m(-3). Diel RGM variations were negatively related to GEM. In the rain, the sum of all Hg species in the unfiltered (HgTUNF) averaged 16 +/- 112 pmol L-1. Temporal distribution of HgTUNF exhibited a pattern of high concentrations during the late dry seasons (up to 57.5 pmol L-1) and low concentrations (down to 2.7 pmol L-1) in the course of the wet seasons. Unfiltered reactive (HgRUNF), dissolved gaseous (DGM) and monomethyl (MMHgUNF.) Hg constituted 20, 5 and 5% of HgTUNF, respectively. All measured Hg species were positively related and displayed negative relationships with the pH of the rain. In the reservoir surface waters, dissolved total mercury (HgTD) averaged 3.4 +/- 1.2 pmol L-1 of which 10% consisted of DGM. DGM showed a trend of high concentrations during the dry seasons (480 +/- 270 finol L-1 and lower (230 +/- 130 finol L-1) in the course of the wet seasons. Diel variations included diurnal photo-induced DGM production (of about 60 firiol L-1 h(-1)) coupled to minute to hour oxidation/ reduction cycles (of > 100 firiol L-1 amplitude). Finally, calculated atmospheric Hg inputs to the Petit-Saut reservoir represented 14 mot yr(-1) whereas DGM evasion reached 23 mol yr(-1). Apportionment among forms of Hg deposition indicated that up to 75% of the total Hg invasive flux follows the rainfall pathway. (C) 2007 Elsevier B.V. All rights reserved.
Science of The Total Environment (0048-9697) (Elsevier), 2007-10 , Vol. 385 , N. 1-3 , P. 132-145

Droits : 2007 Elsevier B.V. All rights reserved
http://archimer.ifremer.fr/doc/2007/publication-3329.pdf
DOI:10.1016/j.scitotenv.2007.06.013
http://archimer.ifremer.fr/doc/00000/3329/

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) : Elsevier
Résumé : To elucidate the origin of the silicic acid (DSi) anomaly observed along the 4000 isobath on the Congo margin, we have established a benthic Si mass balance and performed direct measurements of biogenic silica (bSiO(2)) dissolution in the deep waters and in the sediments. Results strongly suggest that the anomaly originates from the sediments; the intensity of DSi recycling is consistent with the degradation of organic matter, as observed from Si:O-2 ratios in the benthic fluxes compared to that ratio observed in the anomalies. Strong imbalances, observed in both the Si and C mass balances, suggest that the biogenic matter that degrades and dissolves in these sediments near 4000 m does not come from pelagic sedimentation. It is probably not coming also from the deep channel, because observations were similar in the deep channel vicinity (site D) and further south, far from its influence (site C). The composition of the sediments, with an Si:C ratio close to that observed on continental shelves, suggests that this matter is coming from downslope transport. A first estimate of the magnitude of this flux at global scale, close to 12 T mol Si yr(-1), suggests that it may be an important path for transferring Si from land to ocean.
Deep Sea Research Part II: Topical Studies in Oceanography (0967-0645) (Elsevier), 2009-11 , Vol. 56 , N. 23 , P. 2197-2207

Droits : 2009 Elsevier Ltd All rights reserved.
http://archimer.ifremer.fr/doc/2009/publication-7410.pdf
DOI:10.1016/j.dsr2.2009.04.003
http://archimer.ifremer.fr/doc/00000/7410/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Despite many studies, our understanding of silica precipitation from natural waters remains limited, in particular for geothermal waters. Here we present a detailed study on the kinetics of silica polymerization as a function of fluid temperature and pH using high-temperature (250-260 °C) seawater-derived geothermal fluids as those discharged from the Bouillante geothermal site.We monitored the on-site decrease in monomeric silica concentration(initial SiO2 concentration of about 600 mg/l)with time using the molybdenum blue spectrophotometric method on samples of separated water collected from the high-pressure separator at 167 °C and cooled to 25, 50, 75, and 90 °C and for pH values ranging from 5 to 8. During all these experiments, only silica polymerization was observed, with the formation of colloidal particles in suspension in the solutions. No scaling of amorphous silica was formed. The collected data were after modeled in order to determine the useful kinetic parameters for predicting and preventing amorphous silica precipitation in the production wells during fluid exploitation in the specific context of Bouillante. Results under the investigated experimental conditions show that the kinetics of silica precipitation is affected more strongly by pH than by temperature change. The reaction in the acidic Bouillante solution begins with a transition period that significantly decreases the kinetics of silica polymerization. Modeling the experimental data indicates that the silica polymerization up to the state of equilibrium is characterized by a 2nd-order kinetic law relative to dissolved silica; this could indicate that the polymerization is controlled mainly by the formation of dimers. However, the first hour of the experiments is better characterized by a 4th-order kinetic law, suggesting more complex polymerization reactions in the initial stage with the formation of nanocolloidal particles containing 3 to 4 monomers. In both cases, the corresponding kinetics rate constant k is linearly dependent on pH for pH between 5 and 7. The activation energy Ea for the overall reaction, calculated using the Arrhenius equation under the considered pH and temperature conditions, ranges between 41±9.8 and 54±9.6 kJ/mol. To complete this work, the colloid particles formed at the end of the kinetics experiments were extracted and analyzed by SEM and TEM microscopy, X-ray Diffraction and the BET method. Results show that the size of the colloids increase and their specific surface decrease with increasing pH and are thus dependent on pH. Globally, our work provides a reliable database for understanding silica polymerization kinetics in natural geothermal brines or geologic waters characterized by a near neutral pH and moderate dissolved silica concentrations.
ISSN: 0009-2541

hal-01403092
https://hal-brgm.archives-ouvertes.fr/hal-01403092
DOI : 10.1016/j.chemgeo.2016.08.031

Éditeur(s) : Gauthier-Villars
Résumé : The variability of ''yellow substance'' in waters of the Skagerrak and the Kattegat was studied during the international Skagex programme in 1990 and 1991. Data on attenuation of light and fluorescence of dissolved organic matter (DOM) in sea water were collected with a spectral transmissiometer and a submersible fluorometer within a depth range of 0-250 m at several stations. More than fifty-fold variations of fluorescence intensity over space and time were due to the combined action of different sources of DOM in the straits. The surface maximum of fluorescing DOM, related to river outflow, was spreading from Oslo fjord to the central Skagerrak in late spring. This maximum may be ecologically important because it diminishes shortwave PAR. In the autumn the brightest DOM fluorescence was found in the Kattegat and along the Norwegian coast in accordance with earlier studies. The local minima of DOM fluorescence are associated with the Jutland current. Both the instability of the current and a ten-fold difference in DOM content between deep layers of the Skagerrak and Kattegat resulted in strong synoptic variability of fluorescence in the transitional area between the straits. Seasonal and synoptic variabilities of ''yellow substance'' were minimal in the southern Kattegat. The vertical gradients of DOM fluorescence were mostly negative at the depth of the thermocline of the open Skagerrak in spring, reaching values of 40-50 % m-1. Fine structure and complex shape were inherent to fluorescence profiles from areas of intensive water mixing. DOM fluorescence closely covaried with attenuation of UV light: the correlation coefficient was + 0.9 for wavelength w <= 350 nm regardless of season. The inverse dependence between wavelength derivative and magnitude of UV attenuation in the straits did not change with season. DOM fluorescence and water salinity were negatively correlated at depths of 25-50 m but they varied independently in the upper 10 m. No significant correlation between fluorescence and nitrates has been found. Estimates of correlation with phosphates ranged from 0.7 to 0.8. In general, the changes of fluorescence were due to variations of DOM content in sea water but not to variability of DOM composition or state. The properties of DOM fluorescence in the Skagerrak-Kattegat area make it a useful natural tracer of water movements suitable for active remote sensing with airborne lidar.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1993 , Vol. 16 , N. 2 , P. 115-125

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00099/21041/18667.pdf
http://archimer.ifremer.fr/doc/00099/21041/

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Correlations between major and minor transition elements in tectonically emplaced orogenic peridotites have been ascribed to variable degrees of melt extraction and melt–rock reaction processes, leading to depletion or refertilization. To elucidate how such processes are recorded in the subcontinental lithospheric mantle, we processed a large geochemical dataset for peridotites from the four tectono-metamorphic domains of the Beni Bousera orogenic massif (Rif Belt, northern Morocco). Our study reveals that variations in bulk-rock major and minor elements, Mg-number and modal mineralogy of lherzolites, as well as their clinopyroxene trace element compositions, are inconsistent with simple partial melting and mainly resulted from different reactions between melts and depleted peridotites. Up to 30% melting at < 3 GPa and cryptic metasomatism can account for the geochemical variations of most harzburgites. In Grt–Sp mylonites, melting and melt–rock reactions are masked by tectonic mixing with garnet pyroxenites and subsolidus re-equilibration. In the rest of the massif, lherzolites were mostly produced by refertilization of a refractory protolith (Mg-number ∼ 91, Ol ∼ 70%, Cpx/Opx = 0·4) via two distinct near-solidus, melt–rock reactions: (1) clinopyroxene and orthopyroxene precipitation and olivine consumption at melt/rock ratios <0·75 and variable mass ratio between crystallized minerals and infiltrated melt (R), which are recorded fairly homogeneously throughout the massif; (2) dissolution of orthopyroxene and precipitation of clinopyroxene and olivine at melt/rock ratios ≤1 and R = 0·2–0·3, which affected mainly the Ariègite–Seiland and Seiland domains. The distribution of secondary lherzolites in the massif suggests that the first refertilization reaction occurred prior to the differentiation of the Beni Bousera mantle section into petro-structural zones, whereas the second reaction was associated with the development of the tectono-metamorphic domains. Our data support a secondary, refertilization-related origin for most lherzolites in orogenic peridotite massifs.
ISSN: 0022-3530

hal-01526901
https://hal.archives-ouvertes.fr/hal-01526901
DOI : 10.1093/petrology/egx003

Éditeur(s) : Université de Paris 7
Résumé : The Seine estuary and its adjacent region Pays de Caux are two significant sources of mercury for coastal marine environments. It is carried through fluvial means for the Seine bay and through karstic fresh water emergences for Pays de Caux's coastal area. Mercury cycle in the Seine estuary and bay is affected by additional anthropical activities. The estuary's maximal turbidity area acts like a trap and a chemical reactor for fluvial mercury. Within this area, we can confirm: (i) the non conservative behaviour of dissolved mercury; (ii) mercury enrichment of particles when comparing the Seine's and marine environment and we suggest mercury particle redistribution from the organic fraction to the oxyhydroxydes fraction. A large fraction of mercury is exported in this state towards coastal areas. Mercury reduction in surface coastal waters and its atmospherical recycling are major phenomena. Photoreduction and biological reduction play quantitative roles equivalent to total mercury recycling via the atmosphere corresponding approximately to 30 % of fluvial exchanges. We are demonstrating that reactive forms of mercury are supporting photoreduction. Mercury behaviour within Pays de Caux's karst depends of the hydrogeological context of the system (time and flow speed, turbidity, flow); regardless of the speciation and/or partition in underground waters, the total amount of mercury in intertidal areas is quantitatively the same as in the Seine estuary. Mercury brought through intertidal emergences (karstic exudations) is not « filtered » by a maximal turbidity area and is more widely bio-available for mussels than in the Seine estuary. Even being free from growth factor influences through simple models, mussels found in Pays de Caux still show one of the highest mercury contamination on the French coast; for the first time this places the emphasis on how much mercury is brought from underground waters to the coastal environment. Surface complexation modelisation tests are able to reproduce the major part of mercury partition in the Seine estuary and bay if a very low mercury exchangeable fraction and minimum complexation parameters are taken into account; thermodynamic calculations also suggest that a strong or highly concentrated « dissolved » ligand must be present in the water in order to compete with chlorocomplex formations and explain our measures.
L'estuaire de la Seine et la région adjacente du Pays de Caux sont deux sources significatives en mercure pour le milieu marin côtier. Les apports sont d'une part fluviatiles en ce qui concerne la Baie de Seine et karstiques via des émergences d'eau douce pour la zone côtière du Pays de Caux. Le cycle du mercure en estuaire et baie de Seine est perturbé par les apports liés aux activités anthropiques. La zone de turbidité maximum de l'estuaire joue le rôle de piège et de réacteur chimique pour le mercure fluviatile. Au sein de cette zone, nous mettons en évidence : (i) un comportement non-conservatif du mercure dissous; (ii) un enrichissement en mercure des particules par rapport à celles de la Seine et du milieu marin et suggérons une redistribution du mercure particulaire de la fraction organique vers la fraction oxyhydroxydes. C'est sous cette forme qu'une fraction importante du mercure est exportée vers la zone côtière. La réduction du mercure dans les eaux côtières de surface et son recyclage atmosphérique sont des phénomènes majeurs. En effet, la photoréduction et la réduction biologique jouent des rôles quantitativement équivalents avec un recyclage total du mercure via l'atmosphère correspondant à environ 30% des apports fluviatiles. Nous montrons que les formes réactives du mercure constituent le substrat de la photoréduction. Le comportement du mercure au sein du karst du Pays de Caux dépend du contexte hydrogéologiques du système (temps et vitesse de circulation, turbidité, débit) ; quelle que soit la spéciation et/ou la partition dans les eaux souterraines, l'apport en mercure total à la zone intertidale est quantitativement du même ordre de grandeur que les apports de la Seine. Le mercure apporté par les émergences intertidales (exutoires karstiques) n'est pas « filtré » par une zone de turbidité maximale et se trouve plus largement biodisponible pour les moules qu'en estuaire de Seine. En s'affranchissant, par des modèles simples, de l'influences des facteurs de croissance, les moules du Pays de Caux affichent toujours une contamination par le mercure parmi les plus élevées du littoral français; ceci met pour la première fois l'emphase sur l'importance de l'apport en mercure par des eaux souterraines dans un environnement côtier. Les essais de modélisation de complexation de surface reproduisent la majeure partie de la partition du mercure dans l'estuaire et la baie de Seine si l'on tient compte d'une fraction échangeable en mercure très faible et de paramètres de complexation minimums ; les calculs thermodynamiques suggèrent aussi qu'un ligand « dissous » fort ou présent à de fortes concentrations doit être présent dans l'eau afin d'entrer en compétition avec la formation de chlorocomplexes et expliquer nos mesures.

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/2001/these-1842.pdf
http://archimer.ifremer.fr/doc/00000/1842/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A strong non linear relationship between nitrate and organic matter (assessed by dissolved organic carbon, DOC) has been recently demonstrated by Taylor and Townsend (2010), namely for freshwaters. In this context, our study explores this relation from the behavior of sets of normalized UV spectra (same area under each spectrum) of different water samples showing a hidden isosbestic point (HIP) around 225 nm. This HIP is linked to the existence of a simple relation between nitrate and DOC, the proportions of which vary according to the sampling location and environmental factors. In a second step, a simple linear model is proposed for nitrate-DOC relationship (α⋅NO3+β⋅DOC=1) and a validation is proposed for more than 150 samples of different Brittany rivers and lakes. For samples of the largest watershed, a complementary exploitation from data acquired during the different campaigns confirmed the seasonal evolution between spring (high nitrate/low DOC) and autumn (high DOC/low nitrate). Further investigation on other freshwater samples is needed in order to improve the limits of this linear model.
ISSN: 0045-6535

hal-01063932
https://hal.archives-ouvertes.fr/hal-01063932
DOI : 10.1016/j.chemosphere.2014.03.034
PUBMED : 24875878

Éditeur(s) : HAL CCSD Wiley
Résumé : International audience
The way faults control upward fluid flow in nonmagmatic hydrothermal systems in extensional context is still unclear. In the Eastern Pyrénées, an alignment of twenty-nine hot springs (29 ∘ C to 73 ∘ C), along the normal Têt fault, offers the opportunity to study this process. Using an integrated multiscale geological approach including mapping, remote sensing, and macro-and microscopic analyses of fault zones, we show that emergence is always located in crystalline rocks at gneiss-metasediments contacts, mostly in the Têt fault footwall. The hot springs distribution is related to high topographic reliefs, which are associated with fault throw and segmentation. In more detail, emergence localizes either (1) in brittle fault damage zones at the intersection between the Têt fault and subsidiary faults or (2) in ductile faults where dissolution cavities are observed along foliations, allowing juxtaposition of metasediments. Using these observations and 2D simple numerical simulation, we propose a hydrogeological model of upward hydrothermal flow. Meteoric fluids, infiltrated at high elevation in the fault footwall relief, get warmer at depth because of the geothermal gradient. Topography-related hydraulic gradient and buoyancy forces cause hot fluid rise along permeability anisotropies associated with lithological juxtapositions, fracture, and fault zone compositions.
ISSN: 1468-8115

hal-01582968
https://hal-brgm.archives-ouvertes.fr/hal-01582968
https://hal-brgm.archives-ouvertes.fr/hal-01582968/document
https://hal-brgm.archives-ouvertes.fr/hal-01582968/file/Taillefer_et_al_Geofluids_2017.pdf
DOI : 10.1155/2017/8190109

Éditeur(s) : HAL CCSD AGU and the Geochemical Society
Résumé : Geochemistry, Geophysics, Geosystems, v. 9, p. Q12001, 2008. http://dx.doi.org/10.1029/2008GC002098
International audience
Rb/Sr, 40Ar/39Ar, and Sm/Nd isotopic data are reported in Caledonian eclogites from the Lindås Nappe, Bergen Arcs, Norway, in order to investigate processes controlling isotopic equilibrium at mineral scale in polymetamorphic rocks. The Bergen Arcs exposes Sveconorwegian ∼950–930 Ma granulites, partially overprinted by Caledonian eclogite-facies metamorphism at ∼425 Ma and amphibolite-facies metamorphism at ∼410 Ma. Geochemical and Rb-Sr data from more than 10 phengite fractions separated from one sample reflect the composition of the microdomain (a few hundred microns in size) in which phengite crystallized. Phengite crystallized after garnet or plagioclase by dissolution-precipitation processes yield apparent age between 700 and 600 Ma. At the time of their crystallization, these phengites inherited the isotopic composition of their precursor minerals, at a microdomain scale. Phengite from quartz veins, which crystallized from elements mobilized by the circulating fluid, yield an age closer to the eclogite-facies metamorphic age. The closed system evolution of the eclogitizing fluid, the segregation of textural and reactional microdomains, the high Sr content of the studied phengite, and the short duration of the recrystallization processes (<1Ma) are interpreted as the main factors responsible for the lack of a Rb/Sr isotopic equilibrium, at the scale of hand samples. Such equilibrium is nevertheless reached in quartz veins where the crystallization of minerals implies that the fluid circulation acted as a factor of isotopic homogenization. The in situ single mineral Ar/Ar datings revealed that both eclogite- and amphibolite-facies minerals are characterized by an excess of radiogenic argon (ages between 425 and 520 Ma). The excess of argon has been inherited from the previous granulite and has been only partially evacuated from the system by the circulating fluid. The apparent Sm/Nd ages from garnets inherited from the granulite-facies metamorphism (c. 930 Ma) are in agreement with previous estimates. This result confirms that the diffusion of Nd in garnet does not occur at temperatures lower than 700°C. This study highlights the complexity of radiochronometer behavior during HP metamorphism and demonstrates that coupling different radiochronometers, such as Ar/Ar and Rb/Sr, does not always guarantee the validity of the geochronological results.
ISSN: 1525-2027

hal-00407885
https://hal.archives-ouvertes.fr/hal-00407885
DOI : 10.1029/2008GC002098