Spectroscopie Raman résonnante UV in situ à haute température ou à haute pression

Dans cette thèse, la spectroscopie Raman résonante UV (SRRUV) est appliquée pour la première fois à l'étude in situ de matériaux carbonés à très haute température (> 2000 K) ou à haute pression ( 2000 K) or at high pressure (< 1 GPa).The advantages of UVRRS are presented in the first part of this PHD thesis, and used to investigate details of the composition and structure of disordered carbon materials such as: (1) n-type nanocrystalline films, (2) carbonaceous matter in chondrites and (3) tholins, HCN synthetic samples of Titan 's atmosphere. In situ Raman studies are limited to 2000 K by the visible black-body emission. I designed a high temperature cell to perform UVRRS above this limit. The second part of the manuscript presents Raman spectra of pyrolitic graphite and HOPG up to 2700 K. This data are consistent with anharmonic models up to 900 K, and show the coupling effects of electron-phonon and phonon-phonon. The last one dominates the anharmonicity above 1000 K. The Raman spectra was calibrated as a function of temperature and became a thermometer up to 2700 K.For high pressure measurements in the third part, I modified an anvil cell to study by UVRRS, the vibrational changes induced by pressure on very luminescent molecular organic crystals. I present an analysis at 244 nm of resonant Raman modes of perylene crystal under hydrostatic pressure up to 0.8 GPa. Some of them have a non linear feature under pressure, revealing structural and planar modifications of the molecules.LYON-ENS Sciences (693872304) / SudocSudocFranceF

Quantification of water content and speciation in natural silicic glasses (phonolite, dacite, rhyolite) by confocal microRaman spectrometry

International audienceThe determination of total water content (H2OT: 0.1-10 wt%) and water speciation (H2Omolecular/OH) in volcanic products by confocal microRaman spectrometry are discussed for alkaline (phonolite) and calcalkaline (dacite and rhyolite) silicic glasses. Shape and spectral distribution of the total water band (H2OT) at not, vert, similar3550 cm−1 show systematic evolution with glass H2OT, water speciation and NBO/T. In the studied set of silicic samples, calibrations based on internal normalization of the H2OT band to a band related to vibration of aluminosilicate network (TOT) at not, vert, similar490 cm−1 vary with glass peraluminosity. An external calibration procedure using well-characterized glass standards is less composition-dependent and provides excellent linear correlation between total dissolved water content and height or area of the H2OT Raman band. Accuracy of deconvolution procedure of the H2OT band to quantify water speciation in water-rich and depolymerized glasses depends on the strength of OH hydrogen bonding. System confocal performance, scattering from embedding medium and glass microcrystallinity have a crucial influence on accuracy of Raman analyses of water content in glass-bearing rocks and melt inclusions in crystals

Influence of composition and thermal history of volcanic glasses on water content as determined by micro-Raman spectrometry

International audienceDevelopment of Raman spectrometry for quantification of water content in natural glasses requires the assessment of the dependence of the technique on glass composition and thermal history. In the low frequency domain, Raman spectra topology varies due to glass depolymerization and substitution in the framework of (Si4+)IV by alkali-balanced (Al3+)IV and (Fe3+)IV in calcalkaline (rhyolite to basaltic andesite) and alkaline (trachyte, phonolite to alkali basalt) glasses. These processes result in strong dependence of previous analytical procedure (internal calibration) on glass composition. Here, we show that an analytical procedure based on calibration to an external standard is only faintly composition-dependent for Si-rich alkaline glasses (trachytes-phonolites). For a given glass composition, thermal history also plays a fundamental role in the choice of Raman procedure for water analysis. Repeated cycles of thermal annealing induce microcrystallization of hydrous trachyte glasses and modify cation distribution in the glass structure. Application of these concepts to analysis of banded obsidians suggests that small-scale heterogeneities in glasses are not simply related to magma degassing, but could depend on thermal history and consequent relaxation paths in the melt

Source tracing of detrital serpentinite in the Oligocene molasse deposits from the western Alps (Barrême basin): implications for relief formation in the internal zone.

International audienceWe present the first contribution of tracing the source area of ophiolitic detritus in the Alpine molasses by Raman spectroscopy. The lower Oligocene molasse deposits preserved in the Barrême basin, in the SW foreland of the western Alpine arc, are known for the sudden arrival of the first "exotic" detritus coming from the internal Alpine zones. Among them, the pebbles of serpentinized peridotites have so far not been studied. We show that they only consist of antigorite serpentinite, implying that they originate from erosion of HT-blueschists. In contrast, the upper Oligocene/lower Miocene molasse, shows mixed clasts of serpentine including antigorite and lizardite without any evidence of chrysotile. This suggests that they were derived from a less metamorphosed unit such as the LT-blueschist unit. Taking into account the sediment transport direction in the basin and the varied metamorphic characteristics of the other ocean-derived detritus, we constrain the lithological nature of the source zones and the location of the relief zones, identified as the internal Alps, SE of the Pelvoux external crystalline massif. Available structural data and in situ thermochronological data allow reconstructing the Oligocene to early Miocene collisional geometry of the Paleogene subduction wedge. This phase corresponds to two major phases of uplift evolving from a single relief zone located above the Ivrea body during the early Oligocene and persisting up to the early Miocene; then during the late Oligocene/early Miocene a second relief zone developed above the Briançonnais zone. At that time, the internal western Alps acquired its double vergency

Influence of glass polymerisation and oxidation on micro-Raman water analysis in alumino-silicate glasses

International audienceThe development of an accurate analytical procedure for determination of dissolved water in complex alumino-silicate glasses via micro-Raman analysis requires the assessment of the spectra topology dependence on glass composition. We report here a detailed study of the respective influence of bulk composition, iron oxidation state and total water content on the absolute and relative intensities of the main Raman bands related to glass network vibrations (LF: not, vert, similar490 cm−1; HF: not, vert, similar960 cm−1) and total water stretching (H2OT: not, vert, similar3550 cm−1) in natural glasses. The evolution of spectra topology was examined in (i) 33 anhydrous glasses produced by the re-melting of natural rock samples, which span a very large range of polymerisation degree (NBO/T from 0.00 to 1.16), (ii) 2 sets of synthetic anhydrous basaltic glasses with variable iron oxidation state (Fe3+/FeT from 0.05 to 0.87), and (iii) 6 sets of natural hydrous glasses (CH2OT from 0.4 to 7.0 wt%) with NBO/T varying from 0.01 to 0.76. In the explored domain of water concentration, external calibration procedure based on the H2OT band height is matrix-independent but its accuracy relies on precise control of the focusing depth and beam energy on the sample. Matrix-dependence strongly affects the internal calibrations based on H2OT height scaled to that of LF or HF bands but its effect decreases from acid (low NBO/T, SM) to basic (high NBO/T, SM) glasses. Structural parameters such as NBO/T (non-bridging oxygen per tetrahedron) and SM (sum of structural modifiers) describe the matrix-dependence better than simple compositional parameters (e.g. SiO2, Na2O + K2O). Iron oxidation state has only a minor influence on band topology in basalts and is thus not expected to significantly affect the Raman determinations of water in mafic (e.g. low SiO2, iron-rich) glasses. Modelling the evolution of the relative band height with polymerisation degree allows us to propose a general equation to predict the dissolved water content in natural glasses: View the MathML source where CH2OT is the total water content (in wt%) dissolved in glass; TOTN represents the computed ILF/IHF variation as a function of the calculated NBO/T and SM parameters; IH2ON is the H2O band height scaled to ratio of the reference bands; k is the linearity spectrometer response on the H2OT band in function of water content. The water concentrations of the reference glasses are reproduced using this equation with a standard deviation of 0.06 wt%. The adopted parameterisation provides a useful tool towards the characterisation of composition dependence of micro-Raman procedures for silicate glasses. We show, based on the widest range of glass compositions so far investigated, that accurate evaluation of dissolved water content is achieved by micro-Raman spectroscopy

High pressure behavior of CsC8 graphite intercalation compound

International audienceThe high pressure phase diagram of CsC8 graphite intercalated compound has been investigated at ambient temperature up to 32 GPa. Combining X-ray and neutron diffraction, Raman and X- ray absorption spectroscopies, we report for the first time that CsC8, when pressurized, undergoes phase transitions around 2.0, 4.8 and 8 GPa. Possible candidate lattice structures and the transition mechanism involved are proposed. We show that the observed transitions involve the structural re- arrangement in the Cs sub-network while the distance between the graphitic layers is continuously reduced at least up to 8.9 GPa. Around 8 GPa, important modifications of signatures of the electronic structure measured by Raman and X-ray absorption spectroscopies evidence the onset of a new transition

The SuperCam Remote Sensing Instrument Suite for Mars 2020

International audienceThe Mars 2020 rover, essentially a structural twin of MSL, is being built to a) characterize the geology and history of a new landing site on Mars, b) find and characterize ancient habitable environments, c) cache samples for eventual return to Earth, and d) demonstrate in-situ production of oxygen needed for human exploration. Remote-sensing instrumentation is needed to support the first three of these goals [1]. The SuperCam instrument meets these needs with a range of instrumentation including the highest-resolution remote imaging on the rover, two different techniques for determining mineralogy , and one technique to provide elemental compositions. All of these techniques are co-boresighted, providing rapid comprehensive characterization. In addition, for targets within 7 meters of the rover the laser shock waves brush away the dust, providing cleaner surfaces for analysis. SuperCam will use an advanced version of the AEGIS robotic target selection software

The SuperCam Instrument Suite on the Mars 2020 Rover: Science Objectives and Mast-Unit Description

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2-7 m, while providing data at sub-mm to mm scales. We report on SuperCam's science objectives in the context of the Mars 2020 mission goals and ways the different techniques can address these questions. The instrument is made up of three separate subsystems: the Mast Unit is designed and built in France; the Body Unit is provided by the United States; the calibration target holder is contributed by Spain, and the targets themselves by the entire science team. This publication focuses on the design, development, and tests of the Mast Unit; companion papers describe the other units. The goal of this work is to provide an understanding of the technical choices made, the constraints that were imposed, and ultimately the validated performance of the flight model as it leaves Earth, and it will serve as the foundation for Mars operations and future processing of the data.In France was provided by the Centre National d'Etudes Spatiales (CNES). Human resources were provided in part by the Centre National de la Recherche Scientifique (CNRS) and universities. Funding was provided in the US by NASA's Mars Exploration Program. Some funding of data analyses at Los Alamos National Laboratory (LANL) was provided by laboratory-directed research and development funds

SuperCam Calibration Targets: Design and Development

SuperCam is a highly integrated remote-sensing instrumental suite for NASA’s Mars 2020 mission. It consists of a co-aligned combination of Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), Visible and Infrared Spectroscopy (VISIR), together with sound recording (MIC) and high-magnification imaging techniques (RMI). They provide information on the mineralogy, geochemistry and mineral context around the Perseverance Rover. The calibration of this complex suite is a major challenge. Not only does each technique require its own standards or references, their combination also introduces new requirements to obtain optimal scientific output. Elemental composition, molecular vibrational features, fluorescence, morphology and texture provide a full picture of the sample with spectral information that needs to be co-aligned, correlated, and individually calibrated. The resulting hardware includes different kinds of targets, each one covering different needs of the instrument. Standards for imaging calibration, geological samples for mineral identification and chemometric calculations or spectral references to calibrate and evaluate the health of the instrument, are all included in the SuperCam Calibration Target (SCCT). The system also includes a specifically designed assembly in which the samples are mounted. This hardware allows the targets to survive the harsh environmental conditions of the launch, cruise, landing and operation on Mars during the whole mission. Here we summarize the design, development, integration, verification and functional testing of the SCCT. This work includes some key results obtained to verify the scientific outcome of the SuperCam system

Detection of nucleotides adsorbed onto clay by UV Resonant Raman spectroscopy: a step towards the search for biosignatures on Mars

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