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The mantle is the largest reservoir of many of the Earth’s volatile species. Detailed isotopic studies of noble gases within the mantle volatiles have demonstrated that they are of a primordial origin, which have been trapped in the mantle since the Earth’s accretion. This original volatile signature has continually evolved over time, due to the production of in situ radiogenic isotopes and through the recycling of surface volatiles back into the mantle (Lupton and Craig, 1975; Holland and Ballentine, 2006). The study of noble gases within magmatic samples has enabled the composition and structure of the mantle to be determined and has distinguished the multiple volatile reservoirs (primordial, crustal, marine etc.) that have contributed to the mantle composition sampled. Together with the halogens (Cl, Br and I) they represent key tracers of volatile transport processes in the Earth. Therefore a combined analytical approach including the halogens and noble gases is not only be able to track the influx of surface volatile into the mantle, but also provide a greater understanding to the fundamental controls of transport, storage and partitioning of volatiles within the mantle. A combined noble gas and halogen study was undertaken on three different geological samples sets to determine how surface volatiles interact with the mantle on a variety of different scales. Firstly continental xenoliths from the Western Antarctic Rift were analysed to establish the role of subduction volatiles in the creation of the rifts volcanic products. The xenoliths have 3He/4He ratios of 7.5RA indicating that the rift is dominated by the rising asthenospheric mantle. However the Br/Cl and I/Cl ratio and heavy noble gases within the xenoliths indicate that marine derived volatiles have been incorporated into the mantle beneath the rift and may have provided and fundamental control on the formation of the rift itself. Secondly the role of surface contamination on mantle samples has been evaluated. A transect along a MOR pillow basalt has been analysed for its halogen concentrations in conjunction with the previously determined noble gases. The outer sections are enriched in Cl relative to Br and I due to the assimilation of a high salinity brine during eruption. In contrast the crystalline interior of the pillow has MORB like Br/Cl and I/Cl ratios but elevated 132Xe/36Ar ratios indicative of the incorporation of pelagic sediments. This small scale analytical approach has shown that submarine pillow basalts are prone to contamination from the surrounding marine environment and provides a method for the identification and quantification of marine contamination. Finally the halogens within olivine phenocrysts from three Emperor Seamounts have been analysed to determine the distribution of the halogens within the lower mantle. The I/Cl ratio of the samples evolves from a MORB-like ratio in the oldest seamount to elevated values similar to sedimentary pore fluids and chondrites in the younger seamounts. This indicates that the Hawaiian mantle plume contains isolated pockets of subducted or primordial material which have been isolated from whole mantle mixing and have therefore retained a halogen signature distinct from the average mantle values.

The lunar regolith is sensitive to the bombardment history of the Moon and contains a wealth of knowledge regarding the types of processes that have modified the lunar crust through time. Noble gases that are produced and trapped in the lunar regolith, as a result of this interaction with the space environment, can be used to determine the cosmic ray exposure age, maturity, shielding depth and antiquity age of lunar regolith samples. This thesis aims to probe this temporal archive to further understand the impact history of the Moon contained within the regolith. Initially, all the published noble gas literature data for the Apollo regolith breccias, drill cores and soils was compiled into a database where trapped and cosmogenic noble gas component were calculated. These data were used to summarise the history of the lunar regolith contained in the Apollo sample archive. A dichotomy between the "ancient" (determined by the antiquity indicator using the 40Ar/36Artr ratio) regolith samples and those formed in more recent times has been described previously (e.g., McKay et al., 1986).The ancient breccias and soils (&gt;~3.5 Ga) have typically experienced limited amounts of surface exposure (i.e., they are 'immature'). Whereas, regolith samples formed in more recent times ( < 3.5 Ga, << 2 Ga) show a range of maturities. It is likely that the difference in maturity between the ancient and younger breccias reflects the changing collisional conditions of the time i.e., impact flux and regolith turnover rates. Here, 12 lunar meteorite regolith breccias were analysed for their noble gas content (Ne, Ar, Xe isotopes) to determine if lunar meteorites show the same difference between (40Ar/36Ar)tr ratio and maturity. Lunar meteorites in this study and previously published data do show the same negative correlation between (40Ar/36Ar)tr ratio and maturity. Furthermore, many of the lunar meteorite samples have (40Ar/36Ar)tr ratio between 1 and 2.5 indicating antiquity ages of approximately 1-2 Ga. This potentially reflects a declining period of random intermediate impacts bracketing the period between the 'ancient' and 'recent' samples. The same techniques were applied to newly discovered lunar meteorite MIL 13317. This included a full petrology description, mineral chemistry, U-Pb and Pb-Pb ages, and analysis of noble gas content to decipher the regolith history of this new sample. The meteorite is a mixture of mare and highland components (including mare basalts, FAN, Mg-suite and KREEP) with ancient ages (~ 4.3Ga) and a complex regolith history (exposure age ~500 to 800 Ma, antiquity age ~1.92 Ga). MIL 13317 is an important addition to the lunar collection as it contains material from previously unsampled areas of the Moon which is interpreted here to be associated with the northern regions of the Procellarum KREEP Terrane. Work was also begun on Apollo 16 regolith breccias using the same analytical techniques. However, due to instrument issues and friable samples much of the work was not completed and will be continued after the PhD. Understanding the data collected here and the techniques used will feed forward to future missions to the Moon to understand noble gas concentrations in the lunar regolith.

Changes in the atmospheric concentration of greenhouse gases and aerosols alter the energy balance of the climate system. CO2 is the most significant anthropogenic greenhouse gas. The primary source of the increased atmospheric concentration of CO2 since the preindustrial period is from fossil fuel exploitation. As the global need for energy is currently met by combustion of fossil fuels it is imperative that a method of reducing the levels of CO2 being emitted is used. Carbon capture and storage (CCS) is the combination of CO2 capture from large point sources, with the transport of CO2 to a suitable geological storage site where it can safely be contained. Geological CCS technology has the potential to a make a significant contribution to a low carbon technology future. As with any technology, it is imperative to identify techniques that could be used to form part of the monitoring programme. In this thesis, the role of chemical and geochemical tracers are investigated during the transport and storage of CO2. For the first part of this research, a review of the natural gas and CO2 pipeline network in North America and United Kingdom has been compiled from published literature and historical experience. Using this information, research was carried out to determine why odourising has been suggested for CO2 pipeline transport and what benefit it would add. Based on experience from natural gas, it is concluded that high pressure pipelines of CO2 through sparsely populated areas could have odourant added, but will gain little safety benefit. However, adding odourant to CO2 gas phase pipes could aid detection of leaks as well improve public assurance and should be considered in more detail. For the second part of this research, a specially constructed flow cell was designed and built to investigate how noble gases could be used as effective early warning tracers for CO2 migration in storage sites. From this equipment, experimental breakthrough curves for noble gases and SF6 travelling through a sample of Fell sandstone in relation to CO2 over a pressure gradient range of 10,000 – 50,000 Pa were generated. Although noble gases are described as conservative tracers, comparing the breakthrough curves over a range of pressure gradients show that they do not behave as simply as previously assumed. These results were then modelled using a one dimensional advective dispersion transport equation to fit curves to the experimental outputs using two different modelling approaches. A statistical approach can derive the input parameters for an analytical approach, which is needed to understand the dispersivity behaviour of the tracers. A set of values for the dispersivity of noble gases, SF6 and CO2 through porous media is presented in this research. Using a baseline value approach, initial arrival times for krypton and xenon from this research suggest that they could be used as a means of detecting CO2 migration. While helium, neon and argon appear to be unsuitable as early warning tracers for initial detection of CO2, this suggests that they can be used as part of mixture to fingerprint individual CO2 storage sites that may be in close proximity to one another. Results from the experimental and modelling analysis, identify a system where preferential paths exist depending on the change in pressure gradient. The different transport channels progress from a Darcy linear flow regime to a non-linear laminar flow. These results propose an explanation for the patterns observed from tracers in large-scale reservoirs but the output values obtained are limited by scale-dependence and would not be suitable for direct upscaling.

L’Agence nationale pour la gestion des déchets radioactifs (Andra) a pour mission d’évaluer la possibilité d’un stockage sûr et réversible des déchets de haute activité et à vie longue (HAVL) en milieu géologique profond. Depuis 1994, l’Andra étudie dans cette optique les propriétés d’une couche argileuse, le Callovo-Oxfordien (COx) située dans l’Est du Bassin Parisien, à la limite des départements de la Meuse et de la Haute-Marne. A l’échelle du secteur d’étude, le COx constitue une couche homogène d’environ 130 mètres d’épaisseur, profonde de 500 mètres en moyenne, encadrée par deux formations calcaires, l’Oxfordien au sommet et le Dogger à la base. Le COx présente des perméabilités très faibles et des propriétés de confinement favorables pour un stockage.Les gaz rares (He, Ne, Ar, Kr et Xe) sont chimiquement inertes, leur couche de valence étant saturée, aucune liaison covalente intramoléculaire n’est généralement possible. De plus, ils possèdent de nombreux isotopes, d’origine différente, ce qui fait d’eux d’excellents traceurs en hydrogéologie. Les concentrations en gaz rares dans les environnements sédimentaires sont contrôlées par la loi de Henry : ils se dissolvent dans l’eau avec laquelle ils sont en contact, et ce en fonction de paramètres tels que la température, la salinité et la pression.Afin de compléter et préciser les propriétés du COx dans une zone de 250 km² autour du Laboratoire souterrain de Meuse/Haute-Marne, appelée « zone de transposition » (ZT), l’Andra a entrepris une campagne de forages entre Novembre 2007 et Juin 2008. Dans le cadre de cette campagne, le COx a été carotté dans quatre forages et échantillonné. L’un des forages a également recoupé l’ensemble de la pile sédimentaire Mésozoïque, depuis l’Oxfordien calcaire jusqu’à la base du Trias (-1600 mètres).Sur les quatre forages de la zone de transposition (A, B, C et D), des échantillons de roches ont été prélevés et conditionnés pour l’analyse en laboratoire des concentrations en gaz rares dissous dans les eaux porales. Les concentrations absolues en gaz rares ont été déterminées par spectrométrie de masse.Les profils en He obtenus pour chaque plateforme de forage présentent la même tendance. Les concentrations en He mesurées dans les eaux porales de la plateforme C sont en moyenne entre 2 et 3 fois plus faibles que pour les autres plateformes, et ainsi comparables aux valeurs mesurées dans le laboratoire souterrain, ce qui suggèrerait une circulation des eaux dans le Dogger comparativement moins lente que dans les autres plateformes de forage. Une modélisation 1-D des profils de concentration en He a permis de valider les mesures analytiques et de confirmer que la forme des profils est contrôlée par les concentrations en He imposées dans le Dogger. Le profil de concentrations en He mesurées dans le forage profond suggère d’une part une influence très faible voire nulle d’un flux d’origine mantellique et d’autre part une isolation des formations triasiques et du Lias adjacent. L’ensemble des résultats obtenus a ainsi permis d’avoir une meilleure connaissance des processus de transferts diffusifs dans la formation du COx et dans les aquifères encaissants. / The French Radioactive Waste Management National Agency (Andra) is studying the possibility of a high level and long lived radioactive waste repository in geological formation. Since 1994, Andra is studying the properties of the Callovo-Oxfordian (COx) argillaceous rock, located in the eastern part of the Paris Basin. In the designated zone, COx is a 130 meters thick clay rich sequence, found at a depth of about 500 meters and encompassed between two aquifers, the Oxfordian limestone above and the Dogger limestone below. Callovo-Oxfordian permeabilities are very low, which is suitable with radioactive waste disposal. Noble gases (He, Ne, Ar, Kr and Xe) are considered as natural tracers, useful in hydrogeology, for several reasons. First, noble gases are nearly chemically inert, and then no reaction occurs between them and other species. Secondly, noble gases have several isotopes and many of them have different origins, so it is possible to distinguish sources terms. Noble gases concentrations in geological formations are controlled by physical properties such as temperature, pressure and salinity. To have more information on the COx properties, Andra has selected four drilling sites in a 250 km2 area around the Underground Research Laboratory. From November 2007 to June 2008, on each site, Callovo-Oxfordian clay and both overlaying (Oxfordian) and underlying (Dogger) limestones were investigated. A 1600 meters deep borehole, reaching the Trias base, allows investigating the whole length of the Mesozoïc sedimentary pile.On each drilling sites (named A, B, C and D), pore water noble gases concentrations were performed by mass spectrometry. Each helium profiles show the same general trends. Helium concentrations measured in the borehole C COx pore water are about 2 to 3 times lower than those observed for the other boreholes, and so comparable with previous measurements in the Underground Laboratory. These lower concentrations for borehole C could suggest differences in water average velocities in Dogger limestone, in comparison with the other ones. Calculations using a 1-D model were done; the results corroborate analytical measurements and confirm that helium diffusion profiles in the COx are controlled by Dogger helium concentrations that were put in the model. The vertical profile of dissolved helium concentration throughout the deep borehole suggest on the one hand that there is no deep crustal flux, and on the other hand that Trias is well isolated from the Lias and Dogger overlaying formations.The whole results obtained in this study provide a better understanding about diffusive transfer processes occurring in the COx and in the surrounding limestone aquifers.

Femtosecond time scale allows us to follow and control atomic and molecular motion. The atomic vibrations happen in the range of femtosecond scale. Thus, femtosecond technology effectively measures the atomic vibration. However, to determine electron motion, one needs to reach sub-femtosecond time scale that is in attosecond time scale. High Harmonic Generation (HHG) is a non-linear process that converts infrared light to shortest wavelength, such as in the XUV regime. HHG allows to explore electronic motion and to control electron dynamics. HHG easily reaches to XUV region and is enabling attosecond pulse generation. In this thesis we focused to generate attosecond pulses by using noble gases and their mixtures. We used only argon gas, only hydrogen molecule and their mixture with neon gas. We wanted to improve the conversion efficiency (10^-6) of the fundamental light into high harmonics. We use Ne and H2 gas mixture to look enhancement of the HHs.

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<p>The main purpose of this thesis is to implement the Gauss--Legendre quadrature for the dispersion coefficient. This has been done and can be now be made with different number of points. The calculations with this implementation has shown that the relativistic impact on helium, neon, argon and krypton is largest for krypton, that has the highest charge of its nucleus. It was also seen that the polarizability of neon as a function of the imaginary angular frequency decreases monotonically from a static value.</p>

The main purpose of this thesis is to implement the Gauss--Legendre quadrature for the dispersion coefficient. This has been done and can be now be made with different number of points. The calculations with this implementation has shown that the relativistic impact on helium, neon, argon and krypton is largest for krypton, that has the highest charge of its nucleus. It was also seen that the polarizability of neon as a function of the imaginary angular frequency decreases monotonically from a static value.

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