Éditeur(s) : HAL CCSD
Résumé : East African Rift (EAR) is the divergent plate boundary. EAR exposes different stages of extension, from early stage rifting in Tanzania to oceanic accretion in Afar (Ethiopia). Manyara basin is the southernmost rift system of the east branch of EAR with recent volcanism (< 1.5 Ma) and a seismic swarm in the lower crust (20 – 40 km). Due to its location and tectonic setting, the Manyara basin offers the opportunity to study the earliest stage of rift initiation. Manyara volcanism is composed of several types of hyper-alkaline lavas as Mg-nephelinites (Mg# > 55) (Labait, Kwaraha), calciocarbonatite (Kwaraha) and evolved nephelinites (Mg# < 35) (Hanang).Mg-nephelinites (Labait and Kwaraha) are primary lavas mainly composed of olivine and clinopyroxene (cpx). Geochemical modelling from trace elements suggests that these primary magmas result from a degree of partial melting < 1 % from a CO2-garnet-phlogopite-bearing peridotite. These magmas have an asthenospheric source at depth > 120 km (lava carries xenoliths with equilibrium conditions > 4 GPa). The minerals were crystallized from a magma with a low H2O content (0.1 and 0.5 wt% H2O). The calciocarbonatite and evolved nephelinites are derived from Mg-nephelinites by fractional crystallization and immiscibility processes. Hanang nephelinites are silica- and alkaline-rich lavas (44.2 – 46.7 wt % SiO2, 9.5 –12.1 wt % Na2O+K2O, respectively) composed by cpx, Ti-garnet, nepheline, apatite and titanite. Complex zonation of cpx (e.g. abrupt change of Mg#, Nb/Ta, and H2O) and trace element patterns of nephelinites record magmatic differentiation involving open system with carbonate-silicate immiscibility and primary melt replenishment. The low H2O content of cpx (3 – 25 ppm wt. H2O) indicates that at least 0.3 wt % H2O was present at depth during carbonate-rich nephelinite crystallization at 340 – 640 MPa and 1050 – 1100 °C. The study of hosted-nepheline melt inclusions from Hanang allows constraining the late magmatic evolution of nephelinites during storage and magma ascent. Melt inclusions are composed by a silicate trachytic glass, a carbonate phase and a shrinkage bubble. Trachytic glass contains high content in CO2 (0.43 wt %, SIMS analyses), sulfur (0.21 – 0.92 wt % S), chlorine (0.28 –0.84 wt % Cl) and H2O low content (< 0.1 wt %, Raman analyses). Immiscibility process leading to the formation of carbonate occurs in a closed system during rapid magma ascent between 200 – 500 MPa. The carbonate phase is a Ca-Na-K-S-rich and anhydrous carbonate (33 wt % CaO, 20 wt % Na2O, 3 wt % K2O, and 3 wt % S). The pre-immiscible liquid has a phonolitic composition with 6 ± 1.5 wt % CO2 at 700 MPa. A preliminary study of melt inclusions by XANES spectroscopy and whole rocks by Mössbauer spectroscopy was used to determine these Manyara lavas were formed at oxidizing conditions (~ ΔFMQ +1.5).The early stage rifting volcanism (Manyara Basin) is characterized by CO2-rich and H2O-poor magmas from at least 120 km below the rift escarpment. The presence of CO2-rich magmas and the small amount of volcanic rocks erupted at the surface may indicate that the storage and percolation of these magmas at depth is a potential trigger for deep seismic swarms.
Le rift Est africain (REA) est une frontière de plaque en extension. Ce rift présente plusieurs stades d’extension, de l’initiation du rift en Tanzanie jusqu’à l’accrétion océanique en Afar. Le bassin de Manyara se situe le plus au sud de branche Est du REA. Il est caractérisé par la présence de volcanisme récent (< 1,5 Ma) et d’un essaim sismique dans la croûte inférieure (20 – 40 km). De par sa localisation et son contexte tectonique, le bassin de Manyara offre l’opportunité d’étudier le stade le plus précoce de l’initiation du rift. Le bassin de Manyara est composé de plusieurs types de laves hyperalcalines, les néphélinites magnésiennes (Mg# > 55) (Labait, Kwaraha), de calciocarbonatite (Kwaraha) et des néphélinites différenciées (Mg# < 35) (Hanang).Les néphélinites magnésiennes (Labait et Kwaraha) sont des laves primaires composées d’olivines et de clinopyroxènes (cpx). La modélisation géochimique des éléments en trace suggère que ces magmas primaires résultent d'un degré de fusion partielle ≤ 1 % à partir d'une péridotite à grenat et phlogopite. Ces magmas proviennent d’une profondeur > 120 km (présence de xénolites avec des conditions d’équilibre > 4 GPa). Les minéraux ont cristallisés à partir d’un magma pauvre en eau (0,1 et 0,5 pds % H2O). La calciocarbonatite et les néphélinites différenciés sont issues des néphélinites magnésiennes par cristallisation fractionnée et processus d’immiscibilité. Les néphélinites du Hanang sont riches en éléments alcalins (9,5 – 12,1 pds % Na2O+K2O) et en silice (44,2 – 46,7 pds% SiO2) et sont composés de cpx, grenat, néphéline, titanite et apatite. La zonation complexe dans les cpx (par exemple, changement brusque de Mg#, Nb/Ta, et H2O) implique une différenciation magmatique en système ouvert avec immiscibilité de liquide carbonaté et silicaté ainsi qu’un remplissage de la chambre magmatique avec des liquides primaires. La faible teneur en eau des cpx (3 – 25 ppm H2O) indique la présence d’un magma pauvre en eau (0,3 pds % H2O) lors de la cristallisation des cpx à des conditions crustales (340 – 640 MPa et 1050 – 1100 °C). L’étude des inclusions vitreuses dans les néphélines de Hanang permet de contraindre l'évolution magmatique tardive des néphélinites et le comportement des éléments volatils (CO2, H2O, S, F, Cl) lors du stockage et de la remontée du magma. Les inclusions vitreuses sont composées d’un verre trachytique, d’une phase carbonatée et d’une bulle de rétraction. Le verre trachytique contient du CO2 (0,43 pds % CO2, analyses SIMS), du soufre (0,21 à 0,92 pds% S), du chlore (0,28 – 0,84 pds % Cl) et très peu d’H2O (< 0,1 pds % H2O, analyses Raman). Le processus d’immiscibilité conduisant à la formation du carbonate se produit dans un système fermé pendant l'ascension rapide du magma, entre 200 – 500 MPa. La phase carbonatée est un carbonate anhydre et riche en Ca-Na-K-S (33 pds % CaO, 20 pds % Na2O, 3 pds % K2O, et 3 pds % S). Le liquide pré-immiscible a une composition phonolitique avec 6 ± 1,5 pds % CO2 à une pression de 700 MPa. Une étude préliminaire des inclusions par spectroscopie XANES et des roches par spectroscopie Mössbauer a permis de déterminer que les laves de Manyara se sont formées à conditions oxydantes (~ ∆FMQ +1,5).À l’initiation du rift, le volcanisme dans le bassin de Manyara est caractérisé par des magmas riches en CO2 et pauvres en H2O issus d’au moins 120 km de profondeur sous l'escarpement du rift. La présence de ces magmas riches en CO2 et la faible quantité de roches volcaniques émises à la surface peuvent indiquer que le piégeage et la percolation de ces magmas en profondeur est un déclencheur potentiel des essaims sismiques profonds.
https://tel.archives-ouvertes.fr/tel-01563231

NNT : 2016MONTT114
tel-01563231
https://tel.archives-ouvertes.fr/tel-01563231
https://tel.archives-ouvertes.fr/tel-01563231v2/document
https://tel.archives-ouvertes.fr/tel-01563231/file/2016_BAUDOUIN_archivage.pdf

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

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

Éditeur(s) : HAL CCSD 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) : Elsevier Science Bv
Résumé : Mechanisms controlling the transfer and retention of silicon (Si) along continental margins are poorly understood, but play a major role in the functioning of coastal ecosystems and the oceanic biological pump of carbon. Deep-sea fans are well recognized as carbon sink spots, but we lack knowledge about the importance of the fans in the global Si cycle. Here, we provide a first estimate of the role played by the Congo deep-sea fan, one of the biggest in the world, in the Si cycle. Sediment cores sampled in the deep-sea fan were analyzed to build a Si mass balance. An exceptionally high accumulation rate of amorphous silica aSiO(2) (2.29 +/- 0.58 mol Si m(-2) y(-1)) was found, due to a high sedimentation rate and the presence of aluminum in the sediments. Although favored by bioirrigation, recycling fluxes remained low (0.3 mol Si m(-2) y(-1)) and reconstructed input fluxes could only be explained by lateral inputs coming from the canyon. Preliminary calculations show that the rapid transport of aSiO(2) through the canyon and the excellent preservation efficiency in the sediments imply that 50% of aSiO(2) river inputs from the Congo River accumulate annually in the deep-sea fan. Si:C ratios in deep-sea fan sediments were very low (0.2) and only three times as high as those measured in the river itself, which suggests that material from the river and the continental shelf was delivered directly through the canyon, with very little time for Si and C cycle decoupling to take place.
Journal Of Marine Systems (0924-7963) (Elsevier Science Bv), 2015-01 , Vol. 141 , P. 71-79

Droits : 2014 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/00251/36242/35797.pdf
DOI:10.1016/j.jmarsys.2014.07.010
http://archimer.ifremer.fr/doc/00251/36242/

Éditeur(s) : Gauthier-Villars
Résumé : During RV Gaveshani cruise No. 235 (August-September, 1993), particulate matter was collected from euphotic and deeper waters in the Bay of Bengal and analysed for biogenic silica (BSi), lithogenic silica (LSi) and particulate organic carbon (POC). Mean depth profiles of BSi showed a minimum in the surface waters and a maximum in the middle depths of the euphotic zone. The deepening of BSi maxima from north to south coincides with the deepening of the thermocline and thickening of the surface layer. In coastal waters, the contribution of BSi to total particulate silica was high (> 80 %); in offshore waters it was 60-70 %. BSi/POC (0.086) and LSi/POC (0.023) ratios show that particulate matter consists mostly of biogenic material, while the BSi/LSi (1.61) ratio revealed the dominance of siliceous phytoplankton in the euphotic zone. High concentrations of BSi (0.49 mu mol l(-1)) and LSi (1.89 mu mol l(-1)) in deeper waters are due to a high sedimentation rate, the resuspension of bottom sediments and the flow of large amounts of riverine siliceous material.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1997 , Vol. 20 , N. 3 , P. 493-500

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00093/20459/18131.pdf
http://archimer.ifremer.fr/doc/00093/20459/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Jacupiranga Complex is one of several Meso-Cenozoic alkaline intrusive complexes along the margins of the intracratonic Paraná Basin in southern Brazil. The complex encompasses a wide range of rock-types, including dunites, wehrlites, clinopyroxenites, melteigites-ijolites, feldspar-bearing rocks (diorites, syenites, and monzonites), lamprophyres and apatite-rich carbonatites. While carbonatites have been extensively investigated over the last decades, little attention has been paid to the silicate rocks. This study presents new geochonological and geochemical data on the Jacupiranga Complex, with particular emphasis on the silicate lithotypes. 40Ar/39Ar ages for different lithotypes range from 133.7 ± 0.5 Ma to 131.4 ± 0.5 Ma, while monzonite zircon analyzed by SHRIMP yields a U-Pb concordia age of 134.9 ± 1.3 Ma. These ages indicate a narrow time frame for the Jacupiranga Complex emplacement, contemporaneous with the Paraná Magmatic Province. Most of the Jacupiranga rocks are SiO2-undersaturated, except for a quartz-normative monzonite. Based on geochemical compositions, the Jacupiranga silicate lithotypes may be separated into two magma-evolution trends: (1) a strongly silica-undersaturated series, comprising part of the clinopyroxenites and the ijolitic rocks, probably related to nephelinite melts and (2) a mildly silica-undersaturated series, related to basanite parental magmas and comprising the feldspar-bearing rocks, phonolites, lamprophyres, and part of the clinopyroxenites. Dunites and wehrlites are characterized by olivine compositionally restricted to the Fo83-84 interval and concentrations of CaO (0.13–0.54 wt%) and NiO (0.19–0.33 wt%) consistent with derivation by fractional crystallization, although it is not clear whether these rocks belong to the nephelinite or basanite series. Lamprophyre dikes within the complex are considered as good representatives of the basanite parental magma. Compositions of calculated melts in equilibrium with diopside cores from clinopyroxenites are quite similar to those of the lamprophyres, suggesting that at least a part of the clinopyroxenites is related to the basanite series. Some feldspar-bearing rocks (i.e. meladiorite and monzonite) show petrographic features and geochemical and isotope compositions indicative of crustal assimilation, although this may be relegated to a local process. Relatively high CaO/Al2O3 and La/Zr and low Ti/Eu ratios from the lamprophyres and calculated melts in equilibrium with cumulus clinopyroxene point to a lithospheric mantle metasomatized by CO2-rich fluids, suggesting vein-plus-wall-rock melting mechanisms. The chemical differences among those liquids are thought to reflect both variable contributions of melting resulting from veins and variable clinopyroxene/garnet proportions of the source.
ISSN: 0895-9811

hal-01583547
https://hal.archives-ouvertes.fr/hal-01583547
DOI : 10.1016/j.jsames.2017.05.009

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Ukrainian shield hosts two Palaeoproterozoic anorthosite-mangerite-charnockite-granite (AMCG) complexes (the Korosten and Korsun-Novomyrhorod complexes) that intruded Palaeoproterozoic continental crust in north-western and central parts of the shield, respectively. We report results of U-Pb zircon and baddeleyite dating of 16 samples from the Korosten plutonic complex (KPC), and 6 samples from the Korsun-Novomyrhorod plutonic complex (KNPC). Fifteen zircon samples from both complexes were also analysed for Hf isotopes. These new, together with previously published data indicate that the formation of the KPC started at c. 1815 Ma and continued until 1743 Ma with two main phases of magma emplacement at 1800–1780 and 1770–1758 Ma. Each of the main phases of magmatic activity included both basic and silicic members. The emplacement history of the KNPC is different from that of the KPC. The vast majority of the KNPC basic and silicic rocks were emplaced between c. 1757 and 1750 Ma; the youngest stages of the complex are represented by monzonites and syenites that were formed between 1748 and 1744 Ma. Both Ukrainian AMCG complexes are closely associated in space and time with mantle-derived mafic and ultramafic dykes. The Hf isotope ratios in the zircons indicate a predominantly crustal source for the initial melts with some input of juvenile Hf from mantle-derived tholeiite melts.The preferred model for the formation of the Ukrainian AMCG complexes involves the emplacement of large volumes of hot mantle-derived tholeiitic magma into the lower crust. This resulted in partial melting of mafic lower-crustal material, mixing of lower crustal and tholeiitic melts, and formation of ferromonzodioritic magmas. Further fractional crystallization of the ferromonzodioritic melts produced the spectrum of basic rocks in the AMCG complexes. Emplacement of the ferromonzodioritic and tholeiitic melts into the middle crust and their partial crystallization caused abundant melting of the ambient crust and formation of the large volumes of granitic rocks present in the complexes.
ISSN: 0301-9268

hal-01622715
https://hal.archives-ouvertes.fr/hal-01622715
DOI : 10.1016/j.precamres.2017.02.009

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Talc is a hydrous magnesium rich layered silicate that is widely disseminated in the Earth from the seafloor to over 100 km depth, in ultra-high pressure metamorphism of oceanic crust. In this paper we determine the single crystal elastic constants at pressures from 0 to 12 GPa of talc triclinic (C 1¯) and monoclinic (C2/c) polytypes using ab initio methods. We find that talc has an extraordinarily high elastic anisotropy at zero pressure that reduces with increasing pressure. The exceptional anisotropy is complemented by a negative Poisson's ratio for many directions in crystal space. Calculations show that talc is not only one of very few common minerals to exhibit auxetic behaviour, but the magnitude of this effect may be the largest reported so far for a mineral. The compression (Vp) and shear (Vs) wave velocity anisotropy is 80% and 85% for the triclinic polytype. At pressures where talc is known be stable in the Earth (up to 5 GPa) the Vp and Vs anisotropy is reduced to about 40% for both velocities, which is still a very high value. Vp is slow parallel to the c-axis and fast perpendicular to it. This remains unchanged with increasing pressure and is observed in both polytypes. The shear wave splitting (difference between fast and slow S-wave velocities) at low pressure has high values in the plane normal to the c-axis, with a maximum near the alow asterisk-axis in the triclinic and the b-axis in the monoclinic polytype. The c-axis is the direction of minimum splitting. The pattern of shear wave splitting does not change significantly with pressure. The volume fraction of talc varies between 11 and 41% for hydrated mantle rocks, but the lack of data on the crystallographic preferred orientation (CPO) precludes a detailed analysis of the impact of talc on seismic anisotropy in subduction zones. However, it is highly likely that CPO can easily develop in zones of deformation due to the platy habit of talc crystals. For random aggregates of talc, the isotropic Vp, Vs and Vp/Vs ratio have significantly lower values than those of antigorite and may explain low-velocity regions in the mantle wedge. Vp/Vs ratios are more complex in anisotropic media because there are fast and slow S-waves, resulting in Vp/Vs1 and Vp/Vs2 ratios for every propagation direction, making interpretation difficult in deformed polycrystalline talc with a CPO. Talc on the subduction plate boundary can strongly influence guided wave velocity as CPO would develop in this region of intense shearing. The very low coefficient of friction (< 0.1) of talc above 100 °C could also explain silent earthquakes at shallow depths (ca 30 km) along the subduction plate boundaries, frequently responsible for tsunami.
ISSN: 0012-821X

hal-00411481
https://hal.archives-ouvertes.fr/hal-00411481
DOI : 10.1016/j.epsl.2008.07.047

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
The interplay between fault zone cataclasis and cementation is important since both processes can drastically reduce the permeability of faults in porous sandstones. Yet the prediction of fault cementation in high-porosity sandstone reservoirs remains elusive. Nevertheless, this process has rarely been investigated in shallowly buried faults (<2 km; T°<80 °C) where its sealing capacity could be acquired early in the geological history of a reservoir. In this paper, the macro- and microscopic analysis of a fault zone in the porous Cenomanian quartz arenite sands of Provence (France) shows that silica diagenesis occurs in the most intensely-deformed cataclastic parts of the fault zone. This fault zone shows 19–48% of its total thickness occupied by low-porosity quartz-cemented cataclastic shear bands whose porosities range from 0 – ca. 5%. The analysis of the weathering profile around the fault zone reveals the presence of groundwater silcretes in the form of tabular, tightly silicified concretions cross-cut by the fault. Detailed transmitted light, cold-cathodoluminescence and scanning electron microscopy analyses of the silica cements (from the fault and the silcrete) reveal that all the silica cements originate from groundwater diagenetic processes. This study therefore shows that silica cementation can occur specifically in fault zones and as groundwater silcrete in the shallow context of a groundwater system, generated at the vicinity of an erosional unconformity.
ISSN: 0191-8141

hal-01278286
https://hal.archives-ouvertes.fr/hal-01278286
DOI : 10.1016/j.jsg.2015.10.001

Éditeur(s) : HAL CCSD Elsevier
Résumé : High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes. The observed variations of the Ni-62/Ni-58, Ni-61/Ni-58, and Ni-60/Ni-58 ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no Ni-60 anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45 parts per thousand per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation. (C) 2007 Elsevier Ltd. All rights reserved.
ISSN: 0016-7037

hal-00408304
https://hal.archives-ouvertes.fr/hal-00408304
DOI : 10.1016/j.gca.2007.06.049

Éditeur(s) : HAL CCSD Public Library of Science
Résumé : International audience
Ro 31-8220 is a potent protein kinase C (PKC) inhibitor belonging to the chemical class of bisindolylmaleimides (BIMs). Various PKC-independent effects of Ro 31-8220 have however been demonstrated, including inhibition of the ATP-binding cassette drug transporter breast cancer resistance protein. In the present study, we reported that the BIM also blocks activity of the solute carrier organic cation transporter (OCT) 1, involved in uptake of marketed drugs in the liver, in a PKC-independent manner. Ro 31-8220, in contrast to other pan-PKC inhibitors such as staurosporine and chelerythrine, was thus shown to cis-inhibit uptake of the reference OCT1 substrate tetraethylammonium in OCT1-transfected HEK293 cells in a concentration-dependent manner (IC50 = 0.18 μM) and without altering membrane expression of OCT1. This blockage of OCT1 was also observed in human hepatic HepaRG cells that constitutionally express OCT1. It likely occurred through a mixed mechanism of inhibition. Ro 31-8220 additionally trans-inhibited TEA uptake in OCT1-transfected HEK293 cells, which likely discards a transport of Ro 31-8220 by OCT1. Besides Ro 31-8220, 7 additional BIMs, including the PKC inhibitor LY 333531, inhibited OCT1 activity, whereas 4 other BIMs were without effect. In silico analysis of structure-activity relationships next revealed that various molecular descriptors, especially 3D-WHIM descriptors related to total size, correspond to key physico-chemical parameters for inhibition of OCT1 activity by BIMs. In addition to activity of OCT1, Ro 31-8220 inhibited those of other organic cation transporters such as multidrug and toxin extrusion protein (MATE) 1 and MATE2-K, whereas, by contrast, it stimulated that of OCT2. Taken together, these data extend the nature of cellular off-targets of the BIM Ro 31-8220 to OCT1 and other organic cation transporters, which has likely to be kept in mind when using Ro 31-8220 and other BIMs as PKC inhibitors in experimental or clinical studies
ISSN: 1932-6203

hal-01255837
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01255837
DOI : 10.1371/journal.pone.0144667
PUBMED : 26657401
PUBMEDCENTRAL : PMC4675551

Éditeur(s) : HAL CCSD Public Library of Science
Résumé : International audience
Pyrethroids are widely-used chemical insecticides, to which humans are commonly exposed, and known to alter functional expression of drug metabolizing enzymes. Limited data have additionally suggested that drug transporters, that constitute key-actors of the drug detoxification system, may also be targeted by pyrethroids. The present study was therefore designed to analyze the potential regulatory effects of these pesticides towards activities of main ATP-binding cassette (ABC) and solute carrier (SLC) drug transporters, using transporter-overexpressing cells. The pyrethroids allethrin and tetramethrin were found to inhibit various ABC and SLC drug transporters, including multidrug resistance-associated protein (MRP) 2, breast cancer resistance protein (BCRP), organic anion transporter polypeptide (OATP) 1B1, organic anion transporter (OAT) 3, multidrug and toxin extrusion transporter (MATE) 1, organic cation transporter (OCT) 1 and OCT2, with IC50 values however ranging from 2.6 muM (OCT1 inhibition by allethrin) to 77.6 muM (OAT3 inhibition by tetramethrin) and thus much higher than pyrethroid concentrations (in the nM range) reached in environmentally pyrethroid-exposed humans. By contrast, allethrin and tetramethrin cis-stimulated OATP2B1 activity and failed to alter activities of OATP1B3, OAT1 and MATE2-K, whereas P-glycoprotein activity was additionally moderately inhibited. Twelve other pyrethoids used at 100 muM did not block activities of the various investigated transporters, or only moderately inhibited some of them (inhibition by less than 50%). In silico analysis of structure-activity relationships next revealed that molecular parameters, including molecular weight and lipophilicity, are associated with transporter inhibition by allethrin/tetramethrin and successfully predicted transporter inhibition by the pyrethroids imiprothrin and prallethrin. Taken together, these data fully demonstrated that two pyrethoids, i.e., allethrin and tetramethrin, can act as regulators of the activity of various ABC and SLC drug transporters, but only when used at high and non-relevant concentrations, making unlikely any contribution of these transporter activity alterations to pyrethroid toxicity in environmentally exposed humans.
ISSN: 1932-6203

hal-01477206
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01477206
DOI : 10.1371/journal.pone.0169480
PUBMED : 28099443

Éditeur(s) : HAL CCSD Elsevier
Résumé : Siberian cratonic mantle
International audience
The processes that control water distribution in nominally anhydrous minerals from peridotites are twofold. Melt depletion will remove water while metasomatism can potentially add water to these minerals. These processes can lead to a wide range of outcomes in water contents, which in turn could play a role in mantle rheology and long-term cratonic root stability. To examine these complexities, water concentrations in minerals from well-characterized peridotites from the Udachnaya kimberlite in the central Siberian craton were analyzed by FTIR. The peridotites span a complete top to bottom cross-section of typical cratonic lithospheric mantle (2-7 GPa and 700-1400 °C). Diffusion modeling of water content profiles across olivine grains shows that water loss during decompression is limited to the 100 μm rims of olivines; the cores preserved their mantle water contents. Water contents range from 6 to 323 ppm wt H2O in olivine, 28-301 ppm H2O in orthopyroxene (opx), 100-272 ppm H2O in clinopyroxene (cpx) and 0-23 ppm H2O in garnet. Melting modeling cannot reproduce the high water contents of cratonic mantle peridotites and any potential partial melting trend must have been erased by later events. The water contents of minerals, however, are correlated with modal abundances of clinopyroxene and garnet, bulk rock FeO, TiO2 and SiO2 as well as with light and middle rare earth elements in clinopyroxene and garnet. These relationships are best interpreted as interaction of residual, melt-depleted peridotites with silicate melt, which produced modal and cryptic metasomatism. Importantly, the water enrichment in the Siberian cratonic mantle took place prior to kimberlite magmatism and eruption. Water addition by metasomatism occurred from pressures >4 GPa all the way to the base of the cratonic root below central Siberia, but was limited to shallower levels (<5 GPa) in the Kaapvaal cratonic lithosphere. The difference in olivine water contents at the deepest levels of the Kaapvaal (<5 ppm H2O) and Siberian (6-323 ppm H2O) cratonic roots may be linked to oxygen fugacity and resulting fluid speciation or, alternatively, to reaction with different metasomatic agents. Calculated viscosities for the deepest Udachnaya samples are similar to those inferred for the asthenosphere. If these xenoliths are representative of the deep cratonic lithosphere, water is not as important a parameter as previously thought in the strength of cratonic lithosphere, otherwise the cratonic root beneath Udachnaya would have been delaminated. Alternatively, the metasomatic xenoliths may not be representative of the Siberian cratonic root and kimberlites preferentially sample cratonic mantle lithosphere material located near, and metasomatized by, melt conduits, which served as channels for upward migration of water-rich melts and fluids including kimberlites. In that case, the cratonic root overall still may have relatively low water contents, which in addition to its less metasomatized (more refractory) and thereby buoyant nature, still play a role in making it strong enough to resist delamination by the surrounding asthenosphere.
ISSN: 0016-7037

hal-01053920
https://hal.archives-ouvertes.fr/hal-01053920
DOI : 10.1016/j.gca.2014.04.011

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

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

Éditeur(s) : HAL CCSD Elsevier
Résumé : Carbon emission at volcanic centers requires a constant balance between output (mostly by volcanism, either at plate boundaries or intraplate) and input (mostly at trench settings) of carbon from and to the Earth's mantle. The form of carbon that resides in the mantle is controlled by depth (pressure) and oxygen fugacity, the latter in turn depending on the depth and the concentration of iron in the mantle. In the shallow, lithospheric mantle, carbon is likely to be present in the oxidized form of CO2 (except under cratons where carbon is reduced to graphite or diamond). Below approximately 90 km, in the asthenosphere, the oxidized form of carbon is carbonate, either mineral or melt, depending on the thermal regime. At depths greater than approximately 150 km, the asthenospheric mantle is too reducing for carbon to stay in its oxidized form and only diamond is present, unless there is sufficient hydrogen to form reduced C–H fluids. Hence, the region located in the depth range of 90 to 150 km deep is where carbonatitic melts can most likely be produced and impregnate the surrounding mantle through metasomatism. The upper bound of this region is called the carbonate ledge. This limit prevents carbonate (either solid or molten) from ascending because of degassing and CO2 liberation. The lower bound is a redox front where redox melting (that is, melting caused by oxidation) may take place in an ascending portion of carbon-containing mantle. Carbonatite eruptions and presence of carbonate mineral inclusions in deep-seated diamonds provide evidence that these boundaries can be trespassed in some cases.An analysis of the experimental data that has bearing on silicate melting in the presence of carbon further shows that the carbonate ledge is a melting curve with a negative or flat Clapeyron (dP/dT) slope. In the carbonated ultrabasic (peridotite) systems, the carbonate ledge is located between ~ 2–3 GPa. The ledge divides the pressure–temperature space into a region of low-pressure silicate melt production, and a high-pressure region where carbonatites can be produced. Carbonatitic melts in equilibrium with mantle peridotite have compositions close to dolomitic (approximately equal amounts of Ca and Mg) with a general trend of becoming markedly more magnesian with increasing pressure. Calcic carbonatites may be stable at pressures < 2 GPa if clinopyroxene is absent. At mantle transition zone pressure range, there seems to be a melting temperature decrease (negative fusion slope), which may be caused by the stabilization of majoritic garnet.The carbonated basic (broadly eclogitic) system is more complex than the peridotitic one, because of the strong control of bulk silicate composition on melting temperatures, and hence, on melt composition. In carbonated eclogite systems, we propose that the effect of bulk composition upon all observed features can perhaps be related to silica super-saturation, or lack thereof. In some cases, high calcium (> 80 mol% CaCO3) melts can be produced, making the melting of carbonated eclogites an appealing scenario for the genesis of calcio-carbonatites in the Earth's mantle. Comparison with modeled pressure–temperature paths of subducted oceanic lithosphere shows that fusion of carbonated eclogite at depths shallower than 200 km should be expected for hot (Cascadian-type) subduction thermal regimes. On the other hand, in the case of cooler thermal regimes (Honshu-type, for instance), subducted carbonates may be stable to greater depths in Earth at trench settings, depending on the bulk composition of the system.Furthermore, high-pressure experiments show evidence of a continuum among carbonatitic, kimberlitic, melilititic, and basaltic liquids, for increasing melting degree of carbonated peridotite. This continuum has not been documented in the case of fusion of carbonated eclogite. It may be present, however, when certain sediments are fused, although the silicate melts are granitic to rhyodacitic instead of being kimberlitic in composition. Additional high-pressure work on phase relations in the simple binary system CaCO3–MgCO3 and specific focus on oxide solubility in the vapor phase have the potential to further clarify phase relations on complex silicate–carbonate systems at mantle conditions.
ISSN: 0009-2541

hal-01277770
https://hal.archives-ouvertes.fr/hal-01277770
DOI : 10.1016/j.chemgeo.2015.05.018

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The active collision zone around Taiwan orogen receives a variety of sedimentary inputs, including terrigenous flux from Taiwan and Chinese rivers, oceanic currents and atmospheric dust. In order to determine the present-day respective contributions of these different sources, we analysed the Pb and Sr isotopic compositions of late Quaternary sediments accumulated offshore east Taiwan. Samples from the Taiwan Coastal Range (andesites, sandstones, conglomerate and Peinan River terraces and suspended loads) have also been analysed to constrain the mean Taiwan isotopic signature. Mixing lines between the different sources of material indicate that the core located in the Okinawa Trough represents a mixture of about 60% of Taiwan, 30% of Chinese Loess and 10% of Yangtze River contributions. The southernmost core, located close to Luzon Are, is influenced by Taiwan (60%) and volcanic material (40%). The Sr and Pb isotopic compositions of samples cored in the Manila Trench and in the Huatung Basin are strongly influenced by the Taiwan signature, while the Ryukyu Trench core samples point to significant but variable contributions of Chinese Loess and Yangtze River. This work also reports Zn isotopic variations in the silicate fraction of these marine core samples. The overall variation in Zn isotopic compositions (expressed as 666 Zn) is greater than 0.3 per mil (parts per thousand) for an analytical precision of +/- 0.05 parts per thousand. The Zn isotopic signal for most of the marine core samples is similar to the literature data measured on sedimentary material, except for the Manila Trench core samples and the older sample from the Huatung Basin: they present values heavier by 0.2-0.3 parts per thousand, close to those obtained on all Taiwan rocks and Peinan River particulates. These results show: 1- the particular characteristics of Taiwan Zn isotopic compositions on a large scale; and: 2- the possible use of Zn isotopes as a tracer of material sources.
ISSN: 0009-2541

hal-00412214
https://hal.archives-ouvertes.fr/hal-00412214
DOI : 10.1016/j.chemgeo.2007.10.024

Éditeur(s) : HAL CCSD Elsevier
Résumé : The slow advance of a crack in soda-silicate glasses was studied at nanometer scale by in-situ and real-time atomic force microscopy (AFM) in a well-controlled atmosphere. An enhanced diffusion of sodium ions in the stress-gradient field at the sub-micrometric vicinity of the crack tip was revealed through several effects: growth of nodules in AFM height images, changes in the AFM tip–sample energy dissipation. The nodules patterns revealed a dewetting phenomenon evidenced by ‘breath figures'. Complementary chemical micro-analyses were done. These experimental results were explained by a two-step process: (i) a fast migration (typical time: few milliseconds) of sodium ions towards the fracture surfaces as proposed by Langford et al. [J. Mat. Res. 6 (1991) 1358], (ii) a slow backwards diffusion of the cations as evidenced in these AFM experiments (typical time: few minutes). Measurements of the diffusion coefficient of that relaxing process were done at room temperature. Our results strengthen the theoretical concept of a near-surface structural relaxation due to the stress-gradient at the vicinity of the crack tip. The inhomogeneous migration of sodium ions might be a direct experimental evidence of the presence of sodium-rich channels in the silicate structure [A. Meyer et al., Phys. Rev. Let. 93 (2004) 027801].
ISSN: 0022-3093

hal-00407634
https://hal.archives-ouvertes.fr/hal-00407634
DOI : 10.1016/j.jnoncrysol.2006.09.034

Éditeur(s) : HAL CCSD BioMed Central
Résumé : International audience
Background: Ameloblastin (AMBN) is a phosphorylated, proline/glutamine-rich protein secreted during enamel formation. Previous studies have revealed that this enamel matrix protein was present early in vertebrate evolution and certainly plays important roles during enamel formation although its precise functions remain unclear. We performed evolutionary analyses of AMBN in order to (i) identify residues and motifs important for the protein function, (ii) predict mutations responsible for genetic diseases, and (iii) understand its molecular evolution in mammals. Results: In silico searches retrieved 56 complete sequences in public databases that were aligned and analyzed computationally. We showed that AMBN is globally evolving under moderate purifying selection in mammals and contains a strong phylogenetic signal. In addition, our analyses revealed codons evolving under significant positive selection. Evidence for positive selection acting on AMBN was observed in catarrhine primates and the aye-aye. We also found that (i) an additional translation initiation site was recruited in the ancestral placental AMBN, (ii) a short exon was duplicated several times in various species including catarrhine primates, and (iii) several polyadenylation sites are present. Conclusions: AMBN possesses many positions, which have been subjected to strong selective pressure for 200 million years. These positions correspond to several cleavage sites and hydroxylated, O-glycosylated, and phosphorylated residues. We predict that these conserved positions would be potentially responsible for enamel disorder if substituted. Some motifs that were previously identified as potentially important functionally were confirmed, and we found two, highly conserved, new motifs, the function of which should be tested in the near future. This study illustrates the power of evolutionary analyses for characterizing the functional constraints acting on proteins with yet uncharacterized structure.
ISSN: 1471-2148

Droits : http://creativecommons.org/licenses/by/
hal-01212816
http://hal.upmc.fr/hal-01212816
http://hal.upmc.fr/hal-01212816/document
http://hal.upmc.fr/hal-01212816/file/s12862-015-0431-0.pdf
DOI : 10.1186/s12862-015-0431-0

Éditeur(s) : HAL CCSD wiley
Résumé : International audience
The slow advance of a crack in sodo-silicate glasses was studied at nanometer scale by in-situ atomic force microscopy (AFM) in a well-controlled atmosphere (N2 and H2O). An enhanced diffusion of sodium ions in the stress-gradient field at the sub-micrometric vicinity of the crack tip was revealed through several effects: growth of nodules in height images, changes in the AFM tip–sample energy dissipation as detected in phase images. Ex-situ chemical micro-analyses completed the AFM measurements. The nodules patterns revealed a dewetting phenomenon evidenced by “breath figures”, i.e. analog to the fogging that occurs when a vapour condenses onto a 'cold' surface [D. Beysens et al., Phys. Rev. Let. 57, 1433 (1986)]. These experimental results were explained by a two-step process: i) a fast migration of sodium ions towards the fracture surfaces as proposed by Langford et al. [J. Mat. Res. 6, 1358 (1991)], ii) a slow backwards diffusion of the cations as evidenced in these AFM experiments (typical time: few minutes). Measurements of the diffusion coefficient of that relaxing process were done at room temperature. Our results strengthen the theoretical concept of a near-surface structural relaxation due to the stress-gradient at the vicinity of the crack tip. Raman and SIMS studies revealed that nodules – for samples studied after exposition to common air - are preferentially covered by an organic overlayer of a carboxylate salt with a long aliphatic chain. The catalytic role of sodium ions in that chemical process is suspected.
Fractography of glasses an ceramics V
Rochester, United States

hal-00408605
https://hal.archives-ouvertes.fr/hal-00408605