Le présent travail porte sur le développement technologique pour déterminer l'âge des sources de radiostrontium à travers du rapport [Zr-90]/[Sr-90], en utilisant les techniques de spectrométrie de masse et scintillation liquide pour quantifier les deux isotopes. Parce que Sr-90 et Zr-90 sont des interférences isobariques en spectrométrie de masse, une séparation radiochimique est nécessaire pour isoler du Zr-90 avant son analyse. Parmi quatre résines commerciales, la résine DGA a fourni la meilleure performance pour isoler le Zr-90 du Sr-90. Des récupérations supérieures à 99% pour le Zr-90 ont été obtenues. La résine DGA était aussi l'approche la plus rapide et la plus efficace pour éliminer les interférences isobariques du Sr-90 et aussi de l’Y-90 potentiellement présents dans des échantillons contenant des niveaux élevés de radioactivité. Des expériences impliquant l’utilisation d’une cellule de collision pour éliminer des interférences isobariques ont fourni des facteurs de décontamination insuffisants pour des applications en criminalistique nucléaire. / In this work, a technological development to determine the age of radioactive strontium sources through the [Zr-90]/[Sr-90] ratio using mass spectrometry and liquid scintillation to quantify both isotopes is presented. Because Sr-90 and Zr-90 are isobaric interferences in mass spectrometry, a radiochemical separation to isolate Zr-90 has been shown to be mandatory prior to analysis. Four commercial resins (AG50W-X9, Dowex1-X8, Sr and DGA resins) were tested to isolate Zr-90 from Sr-90. Best performance was observed for the DGA resin, including recoveries higher than 99% for Zr-90. DGA has also demonstrated to be the faster approach and the most efficient not only to eliminate isobaric interferences from Sr-90, but also from Y-90, potentially present in samples containing high levels of radioactivity. Experiments using a collision cell to eliminate isobaric interferences in a triple quadrupole mass spectrometer (ICP-QQQMS) have also been carried out, but results have demonstrated insufficient decontamination factors for nuclear forensic applications.

Student Number : 0201438A - PhD thesis - School of Geosciences - Faculty of Science / This project focuses on the Upper Critical and Lower Main Zones in the eastern Bushveld Complex, South Africa. Lithological and stratigraphic information show that there are distinct differences at this level between the eastern and western limbs of the complex. Geochemical studies are centred on the Merensky and Bastard Cyclic Units in which the platiniferous Merensky Reef occurs. A major geochemical hiatus occurs in the Bushveld Complex at the level of the platiniferous Merensky Reef, close to the Critical/Main Zone boundary. The origin of this hiatus and its relation to mineralisation has not been fully resolved. Geochemical parameters are investigated that allow minerals in the Merensky and Bastard Cyclic Units to be classified as originating from either Critical or Main Zone magmas. Modelling of element ratios (Ni/Y, Cr/Ni, Cr/Co, Y/Co, Cr/V, Co/V and Cr/MgO) demonstrates the varying reliability of using ratios as geochemcial tools to constrain magma influxes within a chamber. However, it is shown that the Cr/MgO ratio is effective in determining real differences across the Critical/Main Zone boundary that are independent of lithology. In addition, initial Sr isotope ratios for plagioclase are significantly different in Critical and Main Zone rocks. Geochemical data through the Merensky and Bastard Cyclic Units indicate that orthopyroxene that originated from magma with composition like that of the Critical Zone magma sometimes occurs together with plagioclase that originated from Main Zone magma. In detail, in the pyroxenite at the base of the Merensky Unit, both plagioclase and orthopyroxene display Critical Zone signatures, but in the overlying part of the Merensky Cyclic Unit, plagioclase increasingly shows a Main Zone signature, whereas orthopyroxene continues to display a Critical Zone signature. Similarly, in the Bastard pyroxenite, Sr isotopes and absolute Sr in plagioclase display a range of values from Main Zone to Critical Zone, but orthopyroxene consistently displays Critical Zone affinity. These observations of mineral disequilibrium clearly show that the two major minerals in the Merensky and Bastard Cyclic Units were formed from two different, but coexisting, magmas. A model that accounts for this disequilibrium is proposed here. It invokes the influx of Main Zone magma at the level of the base of the Merensky unit that dispalced the Critical Zone magma upward, but the two magmas did not mix. The latter continued to crystallise orthopyroxene which sank through the Main Zone influx, due to its density contrast. These crystals collected on the crystal pile to form the Merensky pyroxenite. The Main Zone magma, into which the cumulus Critical Zone orthopyroxene accumulated, crystallised interstitial plagioclase that had a Main Zone Sr isotopic ratio. Whole-rock, major element geochemical data show that a variable proportion of the plagioclase in both the Merensky and Bastard pyroxenites is cumulus. It is inferred to have accumulated with orthopyroxene and has a Critical Zone initial Sr isotope ratio. Thus the two pyroxenites now yield a mixed Sr isotopic signature of Critical Zone cumulus and Main Zone intercumulus and possibly cumulus plagioclase that varies along strike. Above the two pyroxenites, the Sr signature of the norites and anorthosites of both cyclic units is dominated by cumulus plagioclase from the Main Zone magma. It is concluded that the variations in initial Sr isotope ratios do not result from mixing of magmas, but result from accumulation of orthopyroxene and plagioclase from a higher, isotopically distinct layer of magma into an underlying layer. The Merensky and Bastard Cyclic Units therefore display features of Critical or Main Zone magma characteristics depending upon which chemical parameter is considered. These cycles are therefore classified as a Transitional Unit.

Aquifers are an important storage location and source of fresh groundwater. They may become polluted by a number of contaminants including mobile divalent radionuclides such as strontium-90 which is a byproduct of uranium fission. A method for remediating such divalent radionuclides is sequestration through co-precipitation into calcium carbonate. Calcium carbonate precipitation occurs naturally but can be enhanced by the use of ureolytic microorganisms living within the aquifer. The microbial enzyme urease cleaves ammonia from urea (added as a stimulant to the aquifer) increasing the pH and subsequently pushing the bicarbonate equilibrium towards precipitation. Laboratory experimentation is necessary to better predict field scale outcomes of remediation that is driven by ureolytic calcium carbonate co-precipitation. To aid in such laboratory experiments, I constructed two ureolytic organisms which contain green fluorescent protein (GFP) so that the location of the microbes in relation to media flow paths and precipitation can be viewed by microscopy in a 2- dimensional porous medium flow cell reactor. The reactor was operated with a parallel flow regime where the two influent media would not promote microbially induced calcium carbonate precipitation until they were mixed in the flow cell. A demonstration study compared the results of parallel flow and mixing in the reactor operated with and without one of the GFP-containing ureolytic organisms. The growth and precipitation of calcium carbonate within the reactor pore space altered flow paths to promote a wider mixing zone and a more widely distributed overall calcium carbonate precipitation pattern. This study will allow optimization of remediation efforts of contaminants such as strontium-90 in aquifers. / Graduation date: 2012

Ce travail de thèse a appréhendé les mécanismes de stockage/libération, d’un point de vue élémentaire et isotopique, du calcium (Ca) et du strontium (Sr) sur ou dans des phases minérales communes des sols (minéraux primaires, minéraux argileux, oxy-hydroxydes, carbonate pédogénétiques). Une méthode de mesure robuste du δ88Sr a dû être développée et validée par la mesure de matériaux de références internationaux, pour la plupart jamais mesuré dans la littérature. Les résultats montrent que l’adsorption du Ca sur des minéraux phyllosilicatés génère un fractionnement isotopique par prélèvement préférentiel de l’isotope léger (40Ca) dans nos conditions expérimentales lorsque les minéraux possèdent une charge structurale et une surface spécifique importante et/ou un espace interfoliaire ouvert à l’adsorption de cations hydratés. Une étude sur des rhizolithes en milieu naturel a mis en avant que l’utilisation des isotopes du Ca et du Sr permet un traçage de source et de mécanismes efficaces dans les thématiques touchant au stockage de ces deux éléments dans les sols. / This PhD thesis examined the mechanisms of storage and release, from and elementary and isotopically point of view, of calcium (Ca) and strontium (Sr) onto or into mineral phases commonly encountered within soils (primary minerals, clay minerals, oxy-hydroxides, pedogenic carbonate). A robust δ88Sr measurements method had to be developed in the laboratory and validated by the measurement of international reference materials, mostly never measured in the literature. The results of this work show that Ca adsorption onto phyllosilicate minerals generates a quantifiable isotopic fractionation by preferential uptake of the light isotope (40Ca) under our experimental conditions when the minerals have a significant structural charge and specific surface area and/or an interlayer space open to hydrated cations adsorption. A study on rhizoliths in natural environment has also highlighted that the combination of Ca and Sr isotopes allows an effective tracing of sources and mechanisms in the problematic related to the storage of these two elements within soils.

L’objectif de cette thèse est d’arriver à mieux contraindre les paramètres qui contrôlent les processus d’altération à l’échelle d’un petit bassin versant, en se focalisant plus précisément sur le rôle de l’hydrologie. Pour ce faire, les variations temporelles et spatiales des signatures chimiques et isotopiques (U, Sr) des eaux du bassin versant du Ringelbach (Vosges, France) sont étudiées. Plusieurs sources de ce bassin versant, essentiellement composé d’un granite plus ou moins fracturé, ont été échantillonnées mensuellement sur une période de deux ans, le long d’un profil altitudinal. Ce bassin versant présente également l’avantage d’être équipé de trois forages profonds (allant jusqu’à 150 mètres de profondeur) qui ont permis de prélever à la fois les roches et les eaux profondes. Sur la base de l’interprétation géochimique des eaux, la connectivité des différents compartiments hydrologiques a été évaluée et un schéma de fonctionnement hydrogéochimique est proposé s’appuyant sur une bonne connaissance du contexte géologique. Enfin, un taux d’altération et un flux d’eau sont estimés à partir d’une modélisation de l’évolution du rapport isotopique de l’uranium (234U/238U) le long d’un trajet d’eau. L’originalité de cette étude est également de coupler cette approche de traçage géochimique avec une approche modélisatrice en utilisant le logiciel KIRMAT (Kinetic Reactions and Mass transport) qui intègre les équations des réactions géochimiques (dissolution/précipitation) et les équations de transport (1D). Il est ainsi possible de simuler le transport réactif d’une eau traversant la roche le long d’un certain trajet d’eau. Cette modélisation s’appuie sur la caractérisation minéralogique, des propriétés physiques des échantillons de roches prélevés le long des forages et sur les interprétations géochimiques des eaux. Ainsi, la modélisation de la composition chimique des eaux de sources et des eaux de forages a permis d’affiner la compréhension des processus d’altération, notamment le rôle des phases secondaires précipitées. Celle-ci permet également une meilleure compréhension des phénomènes de couplage entre les différents paramètres qui contrôlent la signature chimique des eaux à l’échelle du bassin versant. / The main goal of the present thesis is to better constrain the parameters that control weathering processes at a small catchment scale, focusing specifically on the role of hydrology. For this purpose, temporal and spatial variations of the chemical and isotopic (U, Sr) water composition of the Ringelbach catchment are studied. Several springs of this catchment whose basement is mainly composed of granite more or less fractured located along an altitudinal profile were monthly sampled over a period of two years. The additional interest of this site is that three deep boreholes (up to 150 meters deep) allow the sampling of both deep rocks and waters. The connectivity of the different hydrological compartments is evaluated based on the geochemical interpretation of water samples. A schematic hydrological functioning is proposed based on a good knowledge of the geological context. Finally, a weathering rate and a water flux are estimated from the modeling of the uranium activity ratio along a water path. The originality of this study lays also in combination of a geochemical and modeling approaches using the software KIRMAT (Kinetic Reactions and Mass transport) that integrates geochemical reactions (dissolution/precipitation) and 1D mass transport equations. It allow to simulate the reactive transport of a fluid through a rock along a given water pathway. This modeling is based on the characterization of the mineralogical and physical properties of the rock, sampled along the boreholes and the geochemical interpretation of the waters. Thus, the modeling of the chemical composition of the spring waters and borehole waters permit to improve the understanding of weathering processes including the role of precipitated secondary phases. It also allows to better understand the interplay of parameters that that control the water chemical signature at the catchment scale.

The presented work entitled "Mobility of Human Populations at the End of the Stone Age" describes, generalizes, summarizes and subsequently evaluates the factors of migratory tendencies in prehistory - for the period of Neolithic over Eneolithic to Early Bronze Age. Emphasis is placed on the clarification of all interdisciplinary issues. Further on a detailed description of individual processes and archaeological approaches to them. As a basis for my own research, a database of data impacted by articles based on the study of strontium isotopes was created. In the next steps, the database was processed using statistical tools and its outputs were contingency tabletables and charts. Spatial assessment and their contexts were conducted in the GIS (Geographic Information System).

La cité d'Alexandrie s'est développée sur un cordon littoral étroit, baigné au sud par le Maryut, lagune du delta du Nil qui s'est trouvée ainsi au coeur de l'économie industrielle et commerciale de la cité et de son arrière-pays depuis l'antiquité jusqu'à aujourd'hui. Dans ce riche contexte géo-archéologique, l'objectif de cette thèse de géomorphologie littorale a été de proposer une clef de lecture environnementale de l'histoire de l'occupation de la région du Maryut. L'analyse bio-sédimentologique des archives sédimentaires datées au radiocarbone, ainsi que la mesure du rapport isotopique du strontium dans des coquilles d'ostracode ont été utilisées pour reconstituer l'évolution hydrologique et géographique de la lagune à l'Holocène. La dépression du Maryut est transgressée par la mer vers 7,5 ka cal. BP. Les apports du Nil deviennent ensuite progressivement dominant dans le budget hydrologique, parallèlement à la progradation du littorale deltaïque. A partir de 5,5 ka cal. BP, nos données décrivent le retour progressif de conditions marines dominantes, associées à la réduction des débits du Nil, dans le contexte de la terminaison de la Période Africaine Humide. Cette lagune marine apparaît pérenne jusque 3ka cal BP, puis, dans le courant du 3ème millénaire BP, les intrants nilotiques redeviennent prépondérant. Ensuite, les archives sédimentaires et les données historiques disponibles décrivent une histoire environnementale contrastée est apparue corrélée à des phases de dynamisme et de récession agricole et met en évidence, selon nous, l'impact croissant des pratiques d'irrigation sur le fonctionnement du Maryut, situé en terminaison de la chaîne hydraulique. / The ancient city of Alexandria was founded upon a narrow beach ridge, washed by the Maryut to the south. This Nile delta lagoon has been at the heart of the industrial and commercial economies of the city from Antiquity through to present day. Against the backdrop of this rich geoarchaeological context, the aim of this coastal geomorphology thesis is to elucidate the environmental history of the Maryut region.We have reconstructed the hydrological and geographical evolution of the lagoon during the Holocene using: (1) bio-sedimentology of radiocarbon-dated sediment archives; and (2) strontium isotopes in ostracod shells. The Maryut basin was transgressed by the sea around 7.5 ka cal. BP. Progressively, Nile inputs became dominant in the lagoon's hydrological budget, concomitant with the coastal progradation of the delta. After 5.5 ka cal. BP, our data attest to a gradual return to dominant marine conditions, which we link to a reduction in Nile flow in the context of the end of the African Humid Period. This marine lagoon seems to have been perennial until 3 ka cal. BP before Nile inflow became dominant, from the 3rd millennium BP until 0.8-0.9 ka cal. BP. The sediment archives and the historical data support an important retraction of the waterbody around 1 ka cal. BP, recorded by evaporite deposits. This was followed by a new highstand around 0.7 ka cal. BP before a retraction centred on 0.3-0.2 ka cal. BP. Since around 2000 years, this contrasting environmental history is correlated with phases of agriculture peaks and recessions and shows the increasing impact of irrigation practices on the functioning of the Maryut, located at the end of the hydrological conveyor.

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