Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A series of graphene oxide (GO) and zinc partially substituted magnetite GO-Fe1-xZnxOy (0 ≤ x ≤ 0.285) catalysts were synthesised through a precipitation-oxidation method. The rate constants for the degradation of acid orange seven (AO7) proceeded at a significant faster rate under UV-irradiation (up to 670%) than the conventional heterogeneous Fenton-like reaction. The resultant catalysts were mesoporous, so there was no mass transfer limitation for AO7 to access active sites in the catalysts. Further, maximum increases of rate constant up to 220% occurred as the zinc molar concentration increased from x = 0 to x = 0.159. GO enhanced to incorporation of zinc into the combined metal oxide, whilst zinc limited crystal growth, thus forming smaller crystallite sizes. These features proved to be essential for the improved catalytic activity of the resultant catalysts. The optimised zinc molar value at x = 0.159 delivered the best catalytic activity. © The Royal Society of Chemistry 2016.
ISSN: 2046-2069

hal-01683215
https://hal.univ-antilles.fr/hal-01683215
DOI : 10.1039/c6ra04068c

Éditeur(s) : HAL CCSD E Schweizerbart Science Publishers
Résumé : The occurrence and preservation of aragonite in eclogite-facies rocks of north-eastern Corsica is linked to an uncommon microtexture. Aragonite exclusively occurs as oriented fibres in garnet crystals of a graphitic, more or less siliceous marble that immediately overlies a serpentinite body of the meta-ophiolitic unit. The arrangement of the fibres is grossly radial, but more clearly sectoral in subhedral garnet, the fibres growing perpendicular to the garnet/matrix interface. Raman mapping reveals that the carbonate is calcite in the matrix and in poikiloblastic garnet cores, and that the fibres in the garnet mantle are aragonite alone in the case of a carbonate matrix, and both aragonite and quartz (in distinct fibres) in a quartz–carbonate matrix. These features are interpreted as prograde intergrowths, the result of garnet nucleation and growth in a calcite and then aragonite matrix (±quartz). Upon further heating and/or decompression, the aragonite matrix transformed back to calcite while the carbonates included in garnet retained their original structure, in spite of the relatively high temperature attained (ca. 500 °C). These aragonite relics are one more example of the preservation of a high-pressure polymorph through mechanical shielding of inclusions in a rigid host. The aragonite–garnet intergrowths are similar to quartz–garnet intergrowths described in amphibolite-facies graphitic schists. They are evidence that oriented inclusions in garnet are not necessarily precipitates (‘exsolutions'). Unlike precipitates, their orientation is controlled more by the shape of the garnet growth front than by symmetry constraints.
ISSN: 0935-1221

hal-00411136
https://hal.archives-ouvertes.fr/hal-00411136
DOI : 10.1127/0935-1221/2008/0020-1892

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study explores the dynamics of porosity and reactive surface area changes during porous limestone dissolution by CO2-rich water. The Sr and Ca concentrations in both the rock and the outlet solution are used to evaluate the reactive surface area changes of the two rock-forming calcites, i.e. micrite grains and sparite crystals, which have different trace element signatures. The geometric surface area measured with X-ray microtomography decreases slightly whereas the reactive surface area increases continuously with increasing porosity from 20.3 to 30.2%. Surprisingly, changes in reactive surface areas are very different between the two calcites. The reactive surface area changes in the micrite are parabolic while the reactive surface area of sparite increases greatly. The numerical model HYTEC is used to model the change in reactive surface areas during the experiment. Different geometrical models are tested. The model based on spherical-grain dissolution and spherical-pore growth fails to reproduce the experimental results, while the sugar-lump model provides reasonable agreement with the experiment.
ISSN: 0009-2541

hal-00445274
https://hal.archives-ouvertes.fr/hal-00445274
DOI : 10.1016/j.chemgeo.2009.01.032

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Carbonation of peridotite is a widespread process in nature, with emerging societal and environmental implications through geological storage of CO2. We studied the micro- and nano-scale structures associated with the carbonation of peridotite pervaded by a CO2-rich water and the induced changes of its hydrodynamic properties. Focused ion beam (FIB) nanotomography was coupled with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. An experimental sample of dunite core percolated by a CO2-rich fluid (pCO2 = 11 MPa) at 160 °C was compared with a naturally carbonated sample from the Atlantic Ridge (Exp. IODP 304). Results of the 8-days percolation experiment show continuous alteration of olivine into magnesite locally associated with a poorly crystalline serpentine-type mineral referred to as proto-serpentine. The experiment is also characterized by an overall decrease in rock porosity (from 7.7 to 6.4%) and permeability (from 8.5 × 10− 16 to 1.7 × 10− 16 m2). The primary inter-granular porosity (1 to 10 μm) is progressively filled with magnesite, leading to the overall decrease of permeability. At the same time, a secondary small-scale porosity (10 nm to 1 μm) is created at the tip of the dissolution features along the (010) cleavage planes of olivine grains. Carbonate crystals grow within these etch-pit structures behind the dissolution front. Dissolution and precipitation occur at a relative rate that maintains the secondary porosity over the timescale of the experiment (i.e. carbonate growth has to be the slowest one). This process is interpreted as an interface coupled dissolution-precipitation mechanism of olivine carbonation. Proto-serpentine is only formed in highly reduced flow areas, such as small olivine etch-pits (10 to 500 nm wide), which are more isolated from CO2 input. SEM-FIB analyses show the 3D preferential orientation of the dissolution-precipitation planes within a given olivine grain. It suggests the formation of lateral connections between the etch-pits (infra-micrometric “channels”) providing access to reactants and removing reaction products at the reaction sites. The experimental results show that olivine dissolution and magnesite precipitation converge to a quasi-steady state resulting in a constant carbonation rate controlled by reaction kinetics and not by mass transfer for this flow regime. The system self-regulates, independently of the porosity change at least during this incipient stage of olivine carbonation. Similar textures are observed in natural samples collected at 170 m-depth in the vicinity of veinlets driving late fluids down into the cooling oceanic lithosphere. This suggests that similar mechanisms are active in nature and can play an important role in the late, low temperature alteration stages of fractured peridotite. These results also highlight the critical role of nm-scale spatial arrangement of dissolution and precipitation features on mass transfers and on the sustainability of olivine carbonation through coupled dissolution-precipitation processes.
ISSN: 0009-2541

hal-01684733
https://hal.archives-ouvertes.fr/hal-01684733
DOI : 10.1016/j.chemgeo.2017.11.013

Éditeur(s) : HAL CCSD
Résumé : International audience
The influence of Mn solute atoms on sub-grain boundary mobilities in Al has been determined by accurate electron backscatter diffraction analysis of the sub-grain sizes and misorientations during recovery annealing. High purity Al-0.1 and 0.3 wt.% Mn alloys were deformed by plane strain compression at room temperature to equivalent strains of 1.8 and annealed in the temperature range 150-300 °C. An original method of image analysis on sub-boundaries from electron backscatter diffraction maps was applied to quantify the sub-grain size distributions. The change in average sub-grain size with time at several temperatures was then used to estimate sub-grain boundary mobilities in both Al-Mn alloys. The activation energies for sub-grain mobility were found to be 48 and 52 and kJ.mol^-1 for the 0.1 and 0.3 % Mn alloys respectively, with the higher Mn alloy exhibiting lower rates. The sub-boundary mobilities are higher than expected from previous similar work on deformed Al-Si crystals. The orientation dependence of sub-grain growth is also examined.
International Journal of Materials Research

emse-00463551
https://hal-emse.ccsd.cnrs.fr/emse-00463551
DOI : 10.3139/146.110057

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : A hypothetical mechanism for the generation of maturation stress in wood was tested experimentally. The hypothesis was that the maturation stress could partly originate in a physical mechanism related to daily changes in water pressure and associated diurnal strains. The matrix of lignin and hemicellulose, deposited in the cell wall during the night, would be put in compression by the effect of water tension during the next day. The cellulose framework, crystallizing during the day, would be put in tension by the decrease in tension at night and subsequent cell-wall swelling. This was tested on young saplings of sugi and beech. Half of the saplings were submitted to continuous lighting, which canceled diurnal strains. Saplings were tilted 40 degrees, and their uprighting movement was measured. The uprighting movement is directly due to the production of reaction wood and the concomitant development of large longitudinal maturation stress. It occurred in the continuously lighted plants at least as much as in control plants. We conclude that the generation of longitudinal maturation stress in tension or compression wood is not directly related to variations in water pressure and diurnal strains.
ISSN: 1435-0211

hal-01031891
https://hal.archives-ouvertes.fr/hal-01031891
DOI : 10.1007/s10086-005-0788-6

Éditeur(s) : HAL CCSD Elsevier
Résumé : Spinel peridotite xenoliths from Persani Mountains, Southeastern Carpathians, Romania, were submitted to deformation by dislocation creep accompanied by dynamic recrystallization under variable stress and temperature conditions. Predominance of low-angle boundaries parallel to (100) with well-defined [Ovw] rotation axes in olivine indicates that subgrain rotation is the main recrystallization mechanism and that dislocation glide occurs mainly in [100]{0k1} systems. Analysis of olivine crystal preferred orientations highlights that recrystallization results in dispersion of the orientations of recrystallized grains relatively to the parent grains. This dispersion may be quantified by a dimension-less dispersion factor defined as the ratio of the random component of the [100] axis distributions between the recrystallized grains and porphyroclasts. This factor is largely independent from the overall fabric strength, the number of grains analyzed, and the recrystallized grain size. The olivine CPO strength and anisotropy at the rock scale, quantified by J-index, are largely controlled by the volume of recrystallized grains, which depends on finite strain. Comparison of olivine CPO in coarse- and fine-grained porphyroclastic peridotites shows that deviatoric stress and temperature conditions play nevertheless a role on the CPO evolution during recrystallization; selective grain growth, which is favored at high temperature and low stresses, does counteract the dispersion produced by the nucleation processes.
ISSN: 0191-8141

hal-00669963
https://hal.archives-ouvertes.fr/hal-00669963
DOI : 10.1016/j.jsg.2011.09.010

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Slices of polycyclic metasediments (marbles and meta-cherts) are tectonically amalgamated with the polydeformed basement of the Dent Blanche tectonic system along a major Alpine shear zone in the Western Alps (Becca di Salé area, Valtournenche Valley). A combination of techniques (structural analysis at various scales, metamorphic petrology, geochronology and trace element geochemistry) was applied to determine the age and composition of accessory phases (titanite, allanite and zircon) and their relation to major minerals. The results are used to reconstruct the polyphase structural and metamorphic histories, comprising both pre-Alpine and Alpine cycles. The pre-Alpine evolution is associated with low-pressure high-temperature metamorphism related to Permo-Triassic lithospheric thinning. In meta-cherts, microtextural relations indicate coeval growth of allanite and garnet during this stage, at ~ 300 Ma. Textures of zircon also indicate crystallisation at HT conditions; ages scatter from 263 to 294 Ma, with a major cluster of data at ~ 276 Ma. In impure marble, U-Pb analyses of titanite domains (with variable Al and F contents) yield apparent 206Pb/238U dates range from Permian to Jurassic. Chemical and isotopic data suggest that titanite formed at Permian times and was then affected by (extension-related?) fluid circulation during the Triassic and Jurassic, which redistributed major elements (Al and F) and partially opened the U-Pb system. The Alpine cycle lead to early blueschist facies assemblages, which were partly overprinted under greenschist facies conditions. The strong Alpine compressional overprint disrupted the pre-Alpine structural imprint and/or reactivated earlier structures. The pre-Alpine metamorphic record, preserved in these slices of metasediments, reflects the onset of the Permo-Triassic lithospheric extension to Jurassic rifting.
ISSN: 0024-4937

hal-00758123
https://hal.archives-ouvertes.fr/hal-00758123
DOI : 10.1016/j.lithos.2012.05.007

Éditeur(s) : HAL CCSD Wiley-Blackwell
Résumé : International audience
Dating the timing of motion on crustal shear zones is of tremendous importance for understanding the assembly of orogenic terranes. This objective is achieved in this paper by combining petrological and structural observations with novel developments in in situ U-Th-Pb geochronology of allanite. A greenschist facies shear zone within the Mont Blanc Massif is documented. Allanite is synkinematic and belongs to the mylonitic assemblage. LA-ICP-MS U-Th-Pb isotope analyses of allanite reveal high contents and highly radiogenic isotopic compositions of the common-Pb component. The use of measured Pb-isotope compositions of associated minerals (feldspars and chlorite) is critical for accurate common-Pb correction, and provides a powerful mechanism for linking allanite growth to the metamorphic assemblage. A mean 208Pb/232Th age of 29.44 ± 0.95 Ma is accordingly taken for synkinematic allanite crystallisation under greenschist facies conditions. This age reflects the timing of the Mont Blanc underthrusting below the Penninic Front and highlights the potential of directly dating deformation with allanite.
ISSN: 0954-4879

hal-00963545
https://hal.archives-ouvertes.fr/hal-00963545
DOI : 10.1111/ter.12066

Éditeur(s) : HAL CCSD
Résumé : 1 p.
International audience
The 12th May 2008 Wenchuan earthquake in the Longmen Shan occurred on a large thrust fault largely inherited from an Indosinian structure itself probably controlled by an older structural heritage of the South China block continental margin. Within the whole northeast Tibet region, such a structural inheritance has had a major impact on the Tertiary deformation. It appears of primary importance to assess the pre-Tertiary tectonic evolution of the main blocks involved to understand the actual deformation in the eastern edge of Tibet. Over the past decades, the Proterozoic to Cenozoic tectonic, metamorphic and geochronologic history of the Longmen Shan and Songpan Garzê area have been largely studied. We present a synthesis of the tectonic evolution of the Songpan Garzê fold and thrust belt from Triassic to present. The Songpan-Garzê belt was formed during closure of a wide oceanic basin ?lled with a thick (5 to 15 km) sequence of Triassic ?yschoid sediments. Closure of the basin due to Triassic subduction involved strong shortening, intense folding and faulting of the Triassic series. A large-scale décollement, that presently outcrops along the eastern boundary of the belt (Danba area), allowed the growth of a wide and thick accretionary wedge. It develops in the Paleozoic and Triassic series and separates the accretionary prism from an autochthonous crystalline basement which shares many similarities with the basement of the Yangtze Craton (0.7-0.9 Ga). To the north and northwest, below the thickened Triassic series of the belt, the composition (oceanic or continental) of the basement remains unknown. During the Indosinian orogeny the emplacement of orogenic granites (220 - 150 Ma) was associated to crustal thickening. The isotopic composition of granitoids shows that their magma source were predominantly derived from melting of the proterozoic basement with varying degrees of sedimentary material and negligible mantle source contribution. In the Danba area, the décollement outcrops in a large tertiary antiform with a NNW-SSE axis. It has been exhumed too in the hanging wall of the NE-SW faults of the Tertiary Longmen-Shan belt that marks the present day transition from the Tibetan plateau to the Sichuan basin. These faults have episodically absorbed signi?cant shortening since the Late Triassic. The amount and precise timing of post-triassic deformation are dif?cult to constrain especially because of the dif?culty to isolate the tertiary thermochronological signal from the protracted late Triassic - Cretaceous thermal history. Nonetheless it is generally accepted that Jurassic - Cretaceous tectonism did not modi?ed the general Triassic architecture of eastern Tibet contrarily to the Tertiary deformation. The long-term cooling histories obtained on Mesozoic granites and on the metamorphic series of the Danba dome are very similar showing a very slow and regular cooling during Jurassic andCretaceous, con?rming the absence of major tectonic event between c.a. 150 and 30 Ma. Low temperature thermochronology data indicate that ?nal exhumation and cooling occurred in theTertiary with an acceleration between 10 and 5 Ma along the major tectonic structures. Within the Longmen Shan range, a total denudation of 7 to 10 km is estimated for the late Cenozoic period. Similar amounts of late Tertiary denudation have been estimated along an east-west section across the Xianshuihe fault
Asian climate and tectonics seminar
Utrecht, Netherlands

insu-00610298
https://hal-insu.archives-ouvertes.fr/insu-00610298
DOI : 10.1016/j.jseaes.2010.03.008