Éditeur(s) : Gauthier-Villars
Résumé : Simple thermodynamics calculations are applied to processes of a rising plume within an environment of an upward directed gradient of viscosity in the uppermost mantle. Four stages of the development of passive margins are described. Following an initial regional uplift strong lateral movements are induced at asthenospheric levels, stretching the overlying lithosphere. In the second stage plume material also enters the low viscosity lower crust, replacing continental material and forming a new, higher crust-mantle boundary by gravitational differentiation. The inital phase lag between the laterally intruding plume material and the rest of the lithosphere disappears once the continent is rifted and sea floor spreading is established (= stage 3). Finally, at stage 4, quiet subsidence, controlled by contraction, sedimentation, and possible phase changes in the lower crust, is established. The sequence described is in accordance with many observations of geology and geophysics. Rising plumes and sinking slabs are considered equivalent expressions of the heat engine earth which determines global tectonics.
Oceanologica Acta, Special issue (0399-1784) (Gauthier-Villars), 1981

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00245/35658/34167.pdf
http://archimer.ifremer.fr/doc/00245/35658/

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 Springer Verlag
Résumé : International audience
Acquiring information is indisputably energy-consuming and conversely, the availability of information permits greater efficiency. Strangely, the scientific community long remained reluctant to establish a physical equivalence between the abstract notion of information and sensible thermodynamics. However, certain physicists such as Szilard and Brillouin proposed: (i) to give to information the status of a genuine thermodynamic entity (k B T ln2 joules/bit) and (ii) to link the capacity of storing information inferred from correlated systems, to that of indefinitely increasing organization. This positive feedback coupled to the self-templating molecular potential could provide a universal basis for the spontaneous rise of highly organized structures, typified by the emergence of life from a prebiotic chemical soup. Once established, this mechanism ensures the longevity and robustness of life envisioned as a general system, by allowing it to accumulate and optimize microstate-reducing recipes, thereby giving rise to strong nonlinearity, decisional capacity and multistability. Mechanisms possibly involved in priming this cycle are proposed.
ISSN: 0169-6149

inserm-00826658
http://www.hal.inserm.fr/inserm-00826658
http://www.hal.inserm.fr/inserm-00826658/document
http://www.hal.inserm.fr/inserm-00826658/file/OLEB-2013.pdf
DOI : 10.1007/s11084-013-9329-2

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The late Carboniferous accretionary system of the South Tianshan orogen (North-Western China) underwent complex structural and polymetamorphic evolution. Combined petrological, geochronological and microstructural analysis of (ultra)high-pressure (UHP) metabasites (eclogites and blueschists) enclosed in metapelites show a relict coarse-grained eclogitic fabric S2 surrounded by a dominant fine-grained eclogite and blueschist facies retrograde fabric S2. The S2 fabric is reworked by upright folds F3 that are responsible for a major shortening of the whole accretionary system. For both the eclogite and blueschist, peak and retrograde P–T conditions have been thermodynamically constrained at 25–26 kbar and 425–500 °C and 10–13 kbar and 500−550 °C respectively, suggesting a shared exhumation history. The garnet-whole rock-amphibole isochron in the blueschist yielded Lu–Hf and Sm–Nd ages of 326.0 ± 2.9 Ma and 318.4 ± 3.9 Ma respectively, interpreted to date the prograde to peak metamorphic assemblage. The retrograde path of the eclogite is characterized by heterogeneous omphacite recrystallization into a mylonitic fine-grained matrix and crystallization of blue amphibole. Microstructures in both pristine porphyroclastic and recrystallized fine-grained domains in the eclogite indicate a gradual evolution from constriction-dominated (L>S-type) to flattening-dominated (S>L-type) type of deformation, increase of fabric intensity reflected by gradually growing M-indexes and the development of lattice preferred orientation (LPO) typical for dislocation creep under slightly hydrated conditions. Recrystallization of the matrix in the blueschist is homogeneous, which indicates a matrix dominated channel flow during exhumation. These LPOs evolutions suggest a significant mechanical coupling with the upper plate concomitant with oroclinal bending of the Kazakh orocline. Lock up of Kazakh orocline is responsible for further stress increase resulting in horizontal shortening of South Tianshan accretionary wedge and development of D3 upright folding and steepening of the whole sequence.
ISSN: 1342-937X

hal-01481263
https://hal.archives-ouvertes.fr/hal-01481263
DOI : 10.1016/j.gr.2016.07.007

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Accessory phases are important hosts of trace elements; allanite may contain >90% of the REE in a bulk rock. The mobility and redistribution of several trace elements, notably HREE, Th, U, and Y is thus controlled by reactions involving allanite and other REE phases, as well as several rock-forming minerals. As these elements are commonly concentrated in mature elastic sediments, a suite of impure quartzite was studied. Two eclogite facies samples from the Monometamorphic Cover Complex of the Sesia Zone (Western Italian Alps) are presented in some detail, as they reveal a remarkably rich spectrum of reaction relationships that involve REE phases.;Two allanite-forming reactions were inferred from textures and phase compositions;(1) monazite + Ca-silicate(?) + fluid -> allanite + apatite + thorite;;(2) monazite + thorite + Ca-silicate(?) + fluid -> Th-rich allanite + auerlite +/- apatite.;Petrographic observations and thermodynamic models suggest that allanite entered the HP assemblage at similar to 530 degrees C and 17-18 kbar during prograde metamorphism.;In one sample, allanite is rimmed by epidote rich in Y and HREE that grew at the expense of xenotime. Two net transfer reactions were derived;(3) xenotime + allanite + fluid -> Y-rich epidote + apatite + thorite;;(4) xenotime + allanite + fluid -> Y-rich epidote + aeschynite + thorite + (phosphate?).;Textural relationships and trace element analyses of coexisting allanite/monazite and xenotime/Y-rich epidote reveal systematic partitioning of the REE. Partition coefficients for the HREE are compatible with equilibrium fractionation, whereas those for the LREE show patterns that seem to be inherited from the precursor phases, in this case zircon with variable LREE composition.
ISSN: 0003-004X

hal-00745674
https://hal.archives-ouvertes.fr/hal-00745674
DOI : 10.2138/am.2012.3832

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
eoproterozoic eclogite and garnet amphibolites, representing retrogressed eclogites, from the Tassendjanet-Tidéridjaouine terrane in the Pan-African Western Hoggar (Tuareg shield, Southern Algeria) form lenses enclosed in 1.8 Ga subalkaline Paleoproterozoic orthogneisses. They lie along a major sinistral shear zone marking the boundary with the Archean/Paleoproterozoic granulitic In Ouzzal terrane and are associated with high-pressure metasediments. According to thermodynamic calculations, peak condition of the eclogitic stage is 650 °C, 20-22 kbar followed by post-peak heating and exhumation at 730 °C, 10-14 kbar and cooling to 610 °C, 7-10 kbar. Their major, trace-element and isotopic compositions are consistent with emplacement of former basalts in the shoulder of a 700-800 Ma continental rift that evolved to an oceanic basin. The eclogite and garnet amphibolites were thus part of the continental portion of a subducting slab that was pulled down by a denser oceanic lithosphere. Sheath and recumbent folds associated with the exhumation of HP units are verging toward the west, meaning that the former slab was dipping to the east. U-Pb zircon dating on metamorphic zircons bordering ilmenite and rutile in the eclogite gave an age of 623 ± 2 Ma, interpreted as the syn-collisional exhumation stage of the high-pressure unit. This event was rapidly followed by transpressional tectonics and abundant magmatism linked to the northward motion of the adjacent In Ouzzal terrane.
ISSN: 0301-9268

hal-01054338
https://hal.archives-ouvertes.fr/hal-01054338
DOI : 10.1016/j.precamres.2014.04.002

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We combined microstructural observations and high-resolution crystallographic preferred orientation (CPO) mapping to unravel the active deformation mechanisms in garnet clinopyroxenites, garnet-spinel websterites, and spinel websterites from the Beni Bousera peridotite massif. All pyroxenites display microstructures recording plastic deformation by dislocation creep. Pyroxene CPOs are consistent with dominant slip on [001]{110} in clinopyroxene and on [001](100) or [001](010) in orthopyroxene. Garnet clinopyroxenites have however high recrystallized fractions and finer grain sizes than spinel websterites. Recrystallization mechanisms also differ: subgrain rotation dominates in garnet clinopyroxenites, whereas in spinel websterites nucleation and growth also contribute. Elongated shapes and strong intracrystalline misorientations suggest plastic deformation of garnet, but CPOs are weak. Clinopyroxene porphyroclasts in spinel websterites show deformation twins underlined by orthopyroxene exsolutions. Thermodynamic calculations indicate that garnet clinopyroxenites deformed at 2.0 GPa and 950-1000 °C and spinel pyroxenites at 1.8 GPa and 1100-1150 °C. The lower temperatures may explain the faster work rates implied by the finer grained microstructures in garnet clinopyroxenites. Greater stresses may have also reduced the competence contrast between garnet and pyroxene in the garnet pyroxenites and, at the outcrop scale, lowered the competence contrast between pyroxenites and peridotites, favoring mechanical dispersion of pyroxenites in the cooler lithospheric mantle.
ISSN: 0191-8141

hal-00750322
https://hal.archives-ouvertes.fr/hal-00750322
DOI : 10.1016/j.jsg.2012.02.019

Éditeur(s) : HAL CCSD European Geosciences Union
Résumé : We propose to assess the error done when temperature is considered as a conservative tracer in fluviokarst studies. As a matter of fact, heat exchanges occur between karstic Conduit System (CS) and Porous Fractured Matrix (PFM) that prevents from using this approximation without caution. The conservative tracer approximation boils down to consider the cooling of CS water by PFM flow in an open thermodynamic system where the CS is bounded by an Adiabatic Wall (AW). The resulting CS water temperature contrasts with the one obtained from more complete models (CW), which also take into account heat conduction within the CS, within the PFM, and from the CS to PFM through CS a Conductive Wall. In order to assess first orders of this error, the dimensionless equations, characteristic of CS cooling by PFM, have been solved thanks to Alternate Finite Difference Implicit methods both in AW and CW configurations. Four groups of dimensionless numbers appear in the various terms of energy and mass equations among which the Peclet and Reynolds numbers depict the large morphologic and hydrologic variability of natural karstic systems. A parametric exploration of the differences between AW and CW models has then been conducted vs. Peclet numbers (Pe numbers varying from 106 to 109, at constant CS Reynolds number) and vs. Reynolds numbers (Red varying from 103 to 107, at constant Peclet number). The error curves bound finite volumes in the Peclet–Reynolds space that converge uniformly to zero for the extreme values of these parameters. However, for Peclet and Reynolds numbers characteristic of realistic fluviokarst configurations, the errors reach finite values, that give first order information assessing the error done by considering temperatures as conservative tracers. Maximum relative errors around 10−2 (in fact 0.0092) have been found varying Pe; while it remained slightly lower than 0.7 × 10−2 varying Red. An illustrative example of the temperature conservative tracer AW approximation is presented with the data obtained from the main morphologic and hydrologic properties of the Cent–Font resurgence (Hérault, France). According to the results, the error reached at the output of the fluviokarst is 0.00613 (for Pe = 1.4993 × 108 and Red = 4.2969 × 104). When rescaled to the physical domain, this error leads to a temperature difference of 1.77 K between the CW and AW configurations.
ISSN: 1812-2108

hal-01358348
https://hal.archives-ouvertes.fr/hal-01358348
https://hal.archives-ouvertes.fr/hal-01358348/document
https://hal.archives-ouvertes.fr/hal-01358348/file/hessd-11-169-2014.pdf
DOI : 10.5194/hessd-11-169-2014

Éditeur(s) : Terrapub
Résumé : A series of empirical expressions for predicting gas hydrate stability, its volume fraction out of pore space and gas hydrate mass-density were established in different systems in consideration of gas composition (CH4, C2H6, H2S) and salinity (NaCl, seawater), and pore size at temperature between 273.15 and 300 K, based on our gas hydrate thermodynamic model (Sultan et al., 2004b, c). Six of the developed expressions for predicting gas hydrate stability were validated against the available published experimental data and they were also compared with other models. At temperature 273.15 to 290.15 K, the ARDPs (Average Relative Deviation of Pressures between the prediction and the experimental data) have shown that these empirical expressions are in agreement with the experimental data as well as other models, indicating their reliability of predicting gas hydrate stability for these systems. At higher temperatures, the empirical predictions for gas hydrate stability do not well reproduce the experimental data, because they are based on van der Waals model. The empirical expressions for predicting gas hydrate stability in the systems of CH4 + H2S + H2O, CH4 + seawater + poresize, CH4 + H2S + NaCl and CH4 + CO2 + NaCl, and for evaluating gas hydrate fraction and its density need further validation due to lack of available published experimental data. However, the empirical expressions for gas hydrate fraction and its density show that the effects of pore size and salinity are negligible; gas hydrate fraction will increase if methane concentration continuously increases relatively in excess of methane solubility and decreases with pressure within gas hydrate stability zone, which is well consistent with data of natural gas hydrates in Cascadia; gas hydrate density tends to increase with ethane percentage and decrease with pressure.
Geochemical Journal (0016-7002) (Terrapub), 2008-03 , Vol. 42 , N. 2 , P. 163-175

Droits : 2008 TERRAPUB. The Geochemical Society of Japan.
http://archimer.ifremer.fr/doc/2008/publication-4958.pdf
http://archimer.ifremer.fr/doc/00000/4958/

Éditeur(s) : HAL CCSD
Résumé : International audience
The purpose of our study is to model a geothermal reservoir. When geothermal reservoir are assumed to be composed of pure water, the transfer of mass and energy is classically described by two balance equations: mass balance equation and the energy balance equation. In addition to those equations, fluid velocity ist classically given by the Darcy law while thermodynamic properties, inferred from theoretical or empirical equations of state, are used to close the mathematical system. Once this system is closed, there exist different solutions. The first one is to solve for pressure and temperature with a variable switch to saturation in the two-phase region (e.g. TOUGH2). The second one is to solve for pressure and enthalpy to increase stability of phase transition between single and two-phase states (e.g. Hydrotherm). We adopted the second option and chose te use a splitting method to get rid of the complexity of coupling equations and a finite volume method for the spatial discretization. Selecting object-oriented languages, we developed a multi-language framework, combining Python, Fortran and a C++ implementation of IAPWS (from the freesteam project) including the supercritical equations, in porous media velocity is given by Darcy law and to close the system physical properties are determined by the IAPWS-IF97 thermodynamic formulation. We resolve the equations in pressure and enthalpy instead of pressure and temperature in order to increase stability and to handle easier the passage from a single-phase to a two-phase system. We solve the system by using a splitting method - to get rid of the complexity of coupling equations - and a finite volume method. We offer some freedom to users thanks to the implementation of several methods like explicit or implicit Euler, Runge-Kutta or BDF2 for time solvers or GMRES and BICGSTAB for the linear solver. We can handle several boundary conditions like no-flow - describing a boundary which can not exchange matter with the exterior - or like a mixed-therm condition - a Dirichlet condition to the pressure and a Dirichlet or an outflow condition to the temperature in order to describe a recharge or a discharge zone - ... We're developing a multi-language framework, combining Python, Fortran and the C++ implementation of IAPWS (from the freesteam project). All these languages are object-oriented. We've applied this simulation model to the dogger in Paris, France, to several one-dimensional systems and a two-dimensional one made by Coumou with the CSMP++ platform. The dogger is a reservoir exploited to produce heat by pumping water at 70 and reinjecting it in the reservoir at 40. In the one-dimensional systems we wanted to observe the process of heat transfer from a higher temperature boundary to a smaller one in a high-energy domain. The last simulation shows the natural convection of water in a fault. For every simulation we compared the solutions we found with an other code (TOUGH2 or CSMP++) and they agreed. The next step will be to model the geothermal plant in Guadeloupe, West Indies. It's the only place in France - and in the West Indies so far - producing electricity with the earth power. The temperature can reach up to 1000 and the pressure range is around a few hundreds MPa. In some surface zones we can see two-phase water at atmospheric pressure. In the 1980s Bouillante was a laboratory for France. Since 1995 Bouillante has given 30GWh electricity a year to the Guadeloupeans.
PROCEEDINGS, Thirty-Ninth Workshop on Geothermal Reservoir Engineering
Stanford, United States

Droits : info:eu-repo/semantics/OpenAccess
hal-00944133
https://hal-brgm.archives-ouvertes.fr/hal-00944133
https://hal-brgm.archives-ouvertes.fr/hal-00944133/document
https://hal-brgm.archives-ouvertes.fr/hal-00944133/file/Copol.pdf

Éditeur(s) : HAL CCSD
Résumé : The Restefond fault, located in the Late Eocene-Early Oligocene Alpine foreland basin, affects the well lithified and low porosity Grès d'Annot. The fault core zone is characterized by the occurrence of highly deformed sandstone lenses. Deformation inside the lenses corresponds to mm to sub-mm-spaced cleavage planes rich in phyllosilicates and up to cm-thick and dm-long quartz-calcite pure extensional veins. The cleavages are mostly composed of newly-formed synkinematic white mica and chlorite. By using thermodynamic thermometers based on the chemical composition of chlorite, a temperature of 200 ± 20 °C of fault activity was computed. This temperature shows that the Restefond fault was active at burial conditions comprised between 6.5 and 8 km, assuming a mean geothermal gradient between 25 and 30 °Ckm−1. The petrophysic properties of sandstones from the core zone and in the hanging and foot wall of the fault were determined on drilled plugs following three spacial directions. The permeability of the highly deformed sandstone from the core zone is about one order of magnitude higher than in the host rock. This increase in permeability occurs in the direction parallel to the S-C structures and is explained by the occurrence of well-connected micropores localized between platy phyllosilicates. This study shows that the fault petrophysic properties are mostly controlled by the precipitation of synkinematic phyllosilicates under deep burial conditions.
Swiss Journal of Geosciences

hal-00795551
https://hal.archives-ouvertes.fr/hal-00795551
DOI : 10.1007/s00015-012-0099-z

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A full equilibrium treatment of molecular aggregation is presented for prototypes of 1D and 3D aggregates, with and without nucleation. By skipping complex kinetic parameters like aggregate size-dependent diffusion, the equilibrium treatment allows to predict directly time-independent quantities such as critical concentrations. The relationships between the macroscopic equilibrium constants for the different paths are first established by statistical corrections and so as to comply with the detailed balance constraints imposed by nucleation, and the composition of the mixture resulting from homogeneous aggregation is then analyzed using the polylogarithm function. Several critical concentrations are distinguished: the residual monomer concentation in equilibrium (RMC) and the critical nucleation concentration (CNC), that is the threshold concentration of total subunits necessary for initiating aggregation. When increasing the concentration of total subunits, the RMC converges more strongly to its asymptotic value, the equilibrium constant of depolymerization, for 3D aggregates and in case of nucleation. The CNC moderately depends on the number of subunits in the nucleus, but sharply increases with the difference between the equilibrium constants of polymerization and nucleation. As the RMC and CNC can be numerically but not analytically determined, ansatz equations connecting them to thermodynamic parameters are proposed
PCCP : Physical chemistry chemical physics

Droits : info:eu-repo/semantics/OpenAccess
hal-01565995
https://hal.archives-ouvertes.fr/hal-01565995
https://hal.archives-ouvertes.fr/hal-01565995/document
https://hal.archives-ouvertes.fr/hal-01565995/file/Aggregates_in_equilibrium.pdf
DOI : 10.1039/c6cp08369b

Éditeur(s) : HAL CCSD Elsevier
Résumé : Le titre a été changé Ancien titre: Roles for local crowding and pressure in counteracting density fluctuations at equilibrium
International audience
What is the probability that all the gas in a box accumulates in the same half of this box? Though amusing, this question underlies the fundamental problem of density fluctuations at equilibrium, which has profound implementations in many physical fields. The currently accepted solutions are derived from the studies of Brownian motion by Smoluchowski, but they are not appropriate for the directly colliding particles of gases. Two alternative theories are proposed here using self-regulatory Bernoulli distributions. A discretization of space is first introduced to develop a mechanism of matter congestion holding for high densities. In a second mechanism valid in ordinary conditions, the influence of local pressure on the location of every particle is examined using classical laws of ideal gases. This approach reveals that a negative feedback results from the reciprocal influences between individual particles and the population of particles, which strongly reduces the probability of atypical microstates. Finally, a thermodynamic quantum of time is defined to compare the recurrence times of improbable macrostates predicted through these different approaches.
Physica A: Statistical Mechanics and its Applications

hal-00920985
https://hal-univ-rennes1.archives-ouvertes.fr/hal-00920985
https://hal-univ-rennes1.archives-ouvertes.fr/hal-00920985v2/document
ARXIV : 1404.6223
DOI : 10.1016/j.physa.2014.03.067

Éditeur(s) : HAL CCSD
Résumé : International audience
The corrosion rates in the presence of some indole derivates, namely, 9H-pyrido[3,4-b]indole (norharmane) and 1-methyl-9H-pyrido[3,4-b]indole (harmane), as inhibitors of C38 steel corrosion inhibitor in 1 M HCl solution, were measured by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques, in the range of temperatures from 25 to 55∘C. Results obtained revealed that the organic compounds investigated have inhibiting properties for all temperatures. The inhibition was assumed to occur via adsorption of the indole molecules on the metal surface. Adsorption of indole derivates was found to follow the Langmuir isotherm. The apparent activation energies, enthalpies, and entropies of the dissolution process and the free energies and enthalpies for the adsorption process were determined by potentiodynamic polarization and electrochemical impedance. The fundamental thermodynamic functions were used to collect important information about indole inhibitory behaviour.
international Journal of Corrosion

hal-01683120
https://hal.univ-antilles.fr/hal-01683120
DOI : 10.1155/2013/139798

Éditeur(s) : HAL CCSD
Résumé : The mantle deformation processes that control the thinning and break-up of continental lithosphere remain poorly understood. Our knowledge is restricted to either lithospheric scale thermo-mechanical models --that use experimentally derived flow laws--, geophysical imaging and/or rare xenoliths from active continental rifts, such as the East African Rift System. The originality of this work relies on the study of the two largest outcrops of diamond facies subcontinental lithospheric mantle in the world: the Beni Bousera and Ronda peridotite massifs in N Morocco and S Spain, respectively. The structures and petrologic and metamorphic zoning preserved in these massifs --implying a polybaric and polythermal evolution-- provides a unique opportunity to investigate the thermo-mechanical evolution of thick subcontinental lithospheric mantle in extensional settings. In this thesis we studied the deformation mechanisms in both peridotites and pyroxenites to constrain the modes of exhumation of subcontinental lithospheric mantle from garnet-, to spinel-, and finally, to plagioclase lherzolite facies conditions. We combined field mapping of tectonometamorphic domains and structural mapping of ductile structures, microstructural analysis, crystal preferred orientations (CPO) measurements and conventional thermobarometric calculations and thermodynamic modeling (Perple_X) to unravel the pressure and temperature conditions of deformation. We showed that exhumation from garnet- to spinel lherzolite facies conditions was accommodated by fast shearing --in thermal disequilibrium--along a lithospheric scale transtensional shear zone. In this context, the petrological zoning and the large temperature gradient (ca. 100ºC/km) preserved in the Beni Bousera massif represent the mechanical juxtaposition of progressively deeper and hotter lithospheric levels at depths of ca. 60 km in the latest Oligocene (ca. 25 Ma). Final exhumation from spinel- to plagioclase facies lherzolite and emplacement into the crust is best recorded in the Ronda massif where it occurred by inversion and lithospheric scale folding of the highly attenuated continental lithosphere in a back-arc region, probably in relation with southward slab rollback and subsequent collision with the palaeo-Maghrebien passive margin in the early Miocene (21-23 Ma).
Les processus de déformation contrôlant l'amincissement de la lithosphère continentale sont encore mal contraints. Nos connaissances sont principalement basées sur la modélisation thermomécanique d'extension à l'échelle de la lithosphère--utilisant des lois rhéologiques derivées expérimentalement, l'imagerie géophysique et l'analyse de xénolithes provenant de rift continentaux actifs à ce jour, tels que le Rift Est-Africain. L'originalité de ce travail reside dans l'étude des deux plus grands massifs de péridotites sous-continentales ayant enregistrées des conditions primaires du facies à diamant: les massifs de Beni Bousera au nord du Maroc et de Ronda au sud de l'Espagne, respectivement. Les structures et la zonation petrologique et métamorphique --impliquant une évolution polybarique et polythermique-- préservéees dans ces massifs offrent une opportunité unique pour étudier l'évolution thermo-mécanique du manteau sous-continental dans un contexte extensif. Dans ce travail, nous avons étudié les mécanismes de déformation des péridotites et des pyroxénites afin de contraindre les modes d'exhumation du manteau lithosphérique sous-continental, depuis des conditions du facies des lherzolites à grenat, jusqu'au facies à spinelle et enfin à plagioclase. Nous avons combiné la cartographie des faciès tectono-métamorphiques et des structures ductiles de déformation, l'analyse des microstructures, la mesure d'orientations préférentielles de réseau (OPR), et la géothermobarométrie conventionelle couplée à la modélisation thermodynamique (PerpleX) afin de contraindre les conditions de pression et température de la déformation. Nous avons montré que l'exhumation précoce du facies à grenat au facies à spinelle était accomodée par une faille transtensive affectant le manteau lithosphérique. Dans ce contexte, la zonation tectono-métamorphique et le gradient thermique important (ca. 100ºC/km) préservés à Beni Bousera résultent de la juxtaposition mécanique de domaines lithosphériques initialement équilibrés à différentes pressions et températures, fossilisée à une profondeur de ca. 60 km durant l'Oligocène supérieur (ca. 25 Ma). L'exhumation finale du facies de lherzolite à spinelle au facies à plagioclase et l'emplacement final dans la croûte, mieux enregistrés dans Ronda, se sont produits par inversion et plissement de la section lithosphérique fortement amincie dans un contexte arrière-arc, probablement lors du retrait vers le sud de la lithosphère subduite et la collision de l'arc avec les paléo-marges maghrébines au Miocène inférieur (21-23 Ma).
https://tel.archives-ouvertes.fr/tel-00767700

tel-00767700
https://tel.archives-ouvertes.fr/tel-00767700
https://tel.archives-ouvertes.fr/tel-00767700/document
https://tel.archives-ouvertes.fr/tel-00767700/file/THESE_Frets.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The deep structure and deformation mechanisms of the Longmen Shan thrust belt (Sichuan, China), at the eastern border of the Tibetan plateau, were largely debated after the devastating Mw 7.9 Wenchuan earthquake (2008). Recent geophysical studies and field investigations have been focused on the active motion of the major Beichuan fault, which ruptured during the earthquake. However, the total exhumation across the fault still remains unclear. In the hanging wall of the Beichuan fault, the South China block is exhumed in the Pengguan massif. Close to the Beichuan fault, the rocks of the Pengguan massif underwent greenschist facies metamorphism associated with brittle-ductile deformation. No metamorphism is observed in the footwall of the fault. In this study, we characterize and date the metamorphic history recorded in the hanging wall of the Beichuan fault in order to constrain the depth and timing of exhumation of the rocks of the Pengguan massif along the fault. A high-resolution petrological approach involving chemical analyses and X-ray maps was used to analyze the micrometric metamorphic minerals. The P-T conditions of the greenschist facies metamorphic event were estimated by an inverse multi-equilibrium thermodynamic approach. The results, 280 ± 30 °C and 7 ± 1 kbar, suggest that the rocks of the Pengguan massif were exhumed from ca. 20 km depth. Our results underline the importance of the thrusting component in the long-term behavior of the Beichuan fault and provide a minimal depth at which the fault is rooted. In situ laser ablation 40Ar/39Ar dating of metamorphic white mica revealed that the greenschist overprint occurred at 135–140 Ma.The Pengguan massif was therefore partially thrusted along the Beichuan fault during the Lower Cretaceous, long before the Eocene-Miocene exhumation phase which is well-constrained by low-temperature thermochronology. Our results provide the first independent depth information for the exhumation history of the Pengguan massif and reveal a previously undocumented Lower Cretaceous tectonic event that marks the onset of the thick-skinned deformation in the external domain of the Longmen Shan (East of the Wenchuan Fault).
ISSN: 0743-9547

hal-01685556
https://hal.archives-ouvertes.fr/hal-01685556
DOI : 10.1016/j.jseaes.2017.04.003

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Melt generation in the continental crust is thought to significantly influence seismic bulk velocities and anisotropy, although existing laboratory data provide limited constraints on such seismic attributes. In this study we measured ultrasonic compressional wave speeds (Vp) and anisotropy during sample compaction, mica-breakdown and melt-generation in synthetic, foliated quartz–muscovite aggregates. Measurements were performed at peak conditions of 300 MPa hydrostatic confining pressure and 750 °C, over a six hour time period, for three separate samples where wave propagation directions were aligned at 0°, 45° and 90° with respect to the foliation plane. The experiments are initially marked by sample compaction and rapid reduction in porosity (from 25% to <2 vol%), with a corresponding increase in Vp. During initial stages of the experiment Vp ranges from 4.65 to 5.45 km/s, depending on the direction of the P wave propagation, resulting in up to ∼16% anisotropy, which originates mainly from the preferred orientation of muscovite and possible incipient melt lenses oriented parallel to foliation. As the experiment progresses the bulk Vp decreases gradually and Vp anisotropy drops from ∼16% to ∼2% after five hours into the experiment. The drop in anisotropy is caused by muscovite-breakdown and increasing amount of partial melting of the aggregate. The bulk velocities are considerably lower than predicted for a mixture of muscovite and β-quartz (stable at 300 MPa and 750 °C). Thermodynamic modeling indicates that mica breakdown and production of melt with ∼2 wt% dissolved water in the aggregate can explain the low Vp, even though β-quartz is stable; the modeled Vp is ∼4.75 km/s at 300 MPa and 750 °C. These ultrasonic attributes signify movement of the melt to fill vacant pores and coating grain boundaries, effectively connecting melt films and reducing seismic anisotropy. The results may apply to regions where crustal melting is on-going, in particular regions of elevated temperature that are only weakly deforming, with coupled anomalously low bulk velocities and seismic anisotropy.
ISSN: 0012-821X

hal-01243569
https://hal.archives-ouvertes.fr/hal-01243569
DOI : 10.1016/j.epsl.2015.05.039

Éditeur(s) : HAL CCSD
Résumé : Geological storage of CO2 is one of diverse technologies being explored to reduce atmospheric carbon fromindustrial processes (i.e. fossil fuel combustion). One of the specific features of CO2 injection is the possibility ofgeochemical reactions (dissolution – precipitation) between mobile reactive brine (e.g. formation water enrichedin CO2) and the host rock during the spatial and temporal evolution of CO2. That leads to modifications in thepore structure, which in turn change the flow dynamics of the reservoir (e.g. the permeability k). Then, thesesstructural modifications can largely control the injectivity, so that the pressure field in the reservoir and also theCO2 propagation. Accordingly, it is crucial to explore the changes in the reservoir properties (e.g. structural andhydrodynamic) induced during a CO2 injection and specially the relationships between them (e.g. k or reactivesurface-Sr versus porosity-φ , k versus rock heterogeneity), for developing predictive modelling tools of thetransport and reaction processes occurring during a CO2 injection and reliable risk assessment. In the case ofcarbonate rocks, the application of the predictive models of transport and reaction is still challenging, because oftheir high heterogeneity so that the incertitude in the reaction kinetics of carbonate minerals.From this perspective, we realized brine-enriched in CO2 percolation experiments through carbonate rocksamples in thermodynamic conditions expected during CO2 injection in deep reservoirs (T = 100°C et P =12MPa). The permeability changes k(t) is monitored during the experiments and the porosity variationφ (t) iscalculated from chemical analyses of the sampled outlet fluids, using ICP-EAS. The pore structure modificationsare investigated from high resolution X ray micro tomography images acquired from the synchrotron ofGrenoble (ESRF). Depending to the dissolution regime, controlled by the reservoir rock fabric and the chemicalcomposition of the brine (e.g. PCO2), we observed that a modification of pore structure can either improve(atypical result in dissolution context) or impair the value of the permeability k.
Le stockage géologique du CO2 est l’une des diverses technologies étant explorées afin deréduire les émissions de carbone atmosphérique des processus industriels (i.e. combustion del’énergie fossile). L’une des spécifiques caractéristiques de l’injection du CO2 en profondeurreste la possibilité de réactions géochimiques (dissolution-précipitation) entre la saumureréactive mobile (e.g. eau de formation enrichie en CO2) et la roche encaissante durantl’évolution spatiale et temporelle du CO2, conduisant à des modifications dans la structure despores et par conséquent dans les propriétés d’écoulement du réservoir (e.g. la perméabilité k).Donc, ces changements structuraux peuvent largement contrôler l’injectivité, ainsi que lechamp de pression dans le réservoir et aussi la propagation du CO2. Il demeure ainsi cruciald’explorer les changement dans les propriétés de réservoirs (e.g. structurales ethydrodynamiques) induits durant une injection de CO2 et explicitement les relations existantesentre eux (e.g. k ou surface réactive-Sr versus porosité-φ , k versus hétérogénéité de la roche),afin de développer des outils de modélisation prédictive des processus de transport etréactionnels se produisant durant une injection de CO2 et d’évaluer de façon fiable les risques.Dans le cas des réservoirs carbonatés, l’application des modèles prédictifs de transport réactifdemeure toujours un enjeu, car contrainte par la forte hétérogénéité en leur sein ainsi que parl’incertitude dans la cinétique de réactions des minéraux carbonatés dans ce contexte. Danscette optique, nous avons réalisé des expériences de percolation à travers des échantillons deroches carbonatées dans les conditions thermodynamiques de stockage en profondeur (T =100°C et P =12 MPa). L’évolution de la perméabilité k(t) est suivie au cours desexpériences ; et la variation de la porosité φ (t) est calculée à partir des résultats d’analyseschimiques au ICP-AES des fluides de sortie échantillonnés. L’investigation des modificationsapportées à la structure des pores est réalisée par le biais de la Micro-Tomographie hauterésolution à rayon X, acquise au synchrotron de Grenoble (e.g. ESRF).Dépendant du régime de dissolution, contrôlé par la fabrique de la roche réservoir et lacomposition chimique de la saumuré chargée en CO2 (e.g. PCO2 engagée), on a observéqu’une modification de la structure de la roche peut soit améliorer soit détériorer (résultatatypique en contexte de dissolution) la valeur de la perméabilité k.
https://hal.archives-ouvertes.fr/tel-01142136

tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136/document
https://hal.archives-ouvertes.fr/tel-01142136/file/thesemangane2013.pdf

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous-Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6 m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (<50 μm in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. δ18O and δD values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P-T conditions of thrust activity. Temperatures of chlorite formation of about 240°C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7 km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic conditions.
ISSN: 0010-7999

hal-00757736
https://hal.archives-ouvertes.fr/hal-00757736
DOI : 10.1007/s00410-011-0718-0

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The minerals constituting the Earth's upper mantle are nominally anhydrous silicates (NAMs). However they do contain hydrogen as a trace element, decorating point defects in their crystalline structure. Experimental petrology and mineralogy have quantified the maximum concentration under several compositional and thermodynamic conditions, but systematic studies on the hydrogen concentration in minerals from mantle-derived rocks have only recently been carried out. Here, we have compiled the distribution of hydrogen in upper mantle peridotite xenoliths, from which several conclusions can be drawn. NAMs from peridotite xenoliths contain a few ppm wt. H2O in their structure. From the current database, the hydrogen concentrations in olivine regularly increase with increasing depth. The amount of hydrogen in NAMs from peridotite xenoliths from subduction contexts is not higher than in other geological context for similar temperature and pressure conditions. The highest hydrogen concentrations is found in peridotitic olivines from cratonic mantle, and are likely due to the depth of origin. The increasing hydrogen concentration in olivine with increasing depth is likely controlled by the increase of H partitioning into olivine at the expense of orthopyroxene as imposed by a decrease in Al content in opx with depth. However, the sparse data could also indicate that the bulk hydrogen concentration slightly increases with depth > 150 km. In this case, it would suggest, locally (Udachnaya for example), a possible increase in water fugacity due to fluid saturation. Even if the most abundant mineral in mantle rocks is olivine, the bulk hydrogen concentration in peridotites is controlled by the amount of hydrogen stored in pyroxenes. However, hydrogen concentration in olivine remains crucial for consequences on physical properties such as rheology and electrical conductivity. Kinetics of hydrogen transport is reviewed and hydrous melt/fluid percolation appears necessary to homogenize the hydrogen distribution at km-scale. Sampling of natural rock specimens is currently biased (e.g., in favor of optically attractive samples) and needs improvement, which will be achieved by increasing sample diversity (all type of grain sizes, lithologies, geological settings) and size of rock samples, as well as advances in analytical techniques. Acquisition of high quality data will be achieved by studying the co-existing minerals in mantle specimens, exploring each sample by linear and mapping measurements, and using appropriate FTIR calibrations for polarized and unpolarized radiation.
ISSN: 0024-4937

hal-01306676
https://hal.archives-ouvertes.fr/hal-01306676
DOI : 10.1016/j.lithos.2015.11.012