Thesis (Ph.D.) -- University of Adelaide, Dept. of Geology, 2000. / Includes bibliographical references (10 leaves).

Thesis (Ph.D.)--Texas Christian University, 2008. / Title from dissertation title page (viewed Aug. 25, 2008). Includes abstract. Includes bibliographical references.

Thesis (MSc)--University of Stellenbosch, 2007. / Bibliography. Also available via the Internet.

Thesis (Ph.D.)--University of Texas at Dallas, 2008. / Includes vita. Includes bibliographical references (leaves 251-275)

Thesis (M.S.)--University of British Columbia, 1963. / Includes bibliographical references (leaves 127-139).

Thesis (Ph. D.)--Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution, 1987. / Funding was provided by the National Science Foundation under grants OCE 15270 and OCE 16082.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1976. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 211-217).

This thesis is concerned with the preparation of regiospecifically labelled compounds by homogeneous metal catalysed hydrogen isotope exchange reactions. The features of homogeneous hydrogen isotope exchange reactions are discussed in Chapter 1, along with other exchange methods; acid, base, heterogenous metal, radiation, enzymic and zeolite catalysis. In Chapter 2, homogeneous rhodium trichloride is investigated for regiospecificity of tritium labeling in a wide range of aromatic compounds. High regiospecificity of labelling ortho to carboxyl, carboxamide and methanamide groups is found, with the regiospecificity determined by 3H nmr spectroscopy. Also discussed is a study to determine whether any other Group VIII metal complexes will catalyse the ortho tritiation of benzoic acid, in addition to rhodium trichloride. The results of detritiation studies performed on benzoic acids using ruthenium acetylacetonate as catalyst as a model for rhodium trichloride are presented in Chapter 3, A possible reaction mechanism is also presented. Finally, an application of the rhodium trichloride system to the labelling of biologically useful molecules is discussed in Chapter 4. The deuteration and tritiation of a number of drugs and metabolites containing known ortho directing groups is described. In a large number of cases, the regiospecificity for ortho labelling is very high.

Isotope tracer techniques are widely used in biological, agricultural, chemical and medical research. The use of stable isotopes is not complicated by health hazards, dangers of radiation or time limit for experiments as is the case for radioactive isotopes. However, the analytical methods available for the determination of stable isotopes are much less sensitive, considerably more complicated and time consuming than those for radioactive isotopes. Such methods usually require the use of a mass spectrometer and most employ the combustion technique (Dumas method) for sample presentation. Speciation can be achieved by an isotope ratio mass spectrometer coupled to a gas chromatograph (GC) and combustion interface. Such instruments are expensive and labour intensive. Additionally, the consumables and catalysts employed are costly.

L’injection de CO2 dans un réservoir géologique n’a rien d’un processus anodin : les impacts sur la roche hôte peuvent menacer l’intégrité du stockage suite à des modifications des propriétés pétrophysiques. Nous proposons ainsi d’envisager l’utilisation des isotopes stables du chlore comme indicateurs des processus physicochimiques générés par une injection de CO2. L’ion chlorure Cl- est en effet un élément conservatif et ubiquiste dans les eaux des réservoirs, et le rapport δ37Cl est connu pour être modifié par divers processus (diffusion, filtration ionique, précipitation de sel, changements de phase). La méthodologie adoptée a consisté à investiguer les effets de ces différents processus sur le signal isotopique du Cl en conditions P-T d’un réservoir de stockage. Des expériences en autoclaves ont montré que le Cl était solubilisé dans le CO2sc, mais en quantités suffisamment faibles pour ne pas impacter le signal isotopique dans les saumures si fractionnement isotopique il y a. Des expériences de migration d’une saumure réactive par advection (banc de percolation ICARE1, Université de Montpellier) et par diffusion (cellule développée à IFPEN) ont également été réalisées. Aucune évolution de δ37Cl n’a été mesurée au cours de la percolation (transport advectif conservatif) et les effets de la diffusion restent à évaluer et à mettre en relation avec les évolutions de porosité et perméabilité des roches. Les expériences de séchage et de précipitation de sel en milieu poreux ont montré que les concentrations en Cl et les valeurs de δ37Cl permettaient de caractériser les processus de transport en jeu. Ces résultats expérimentaux ont permis d’identifier des processus capables de modifier les abondances isotopiques de Cl et indiquent l’intérêt des isotopes pour le monitoring de site de stockage de CO2 / CO2 injection in a reservoir leads to physicochemical processes which can have harmful consequences on the reservoir integrity due to porosity and permeability alteration. In this work, we propose to test the possibility that stable chlorine isotopes could be used as a geochemical tool to assess these effects. Indeed, chloride is a conservative and a major component of reservoir brines, and it is already known that several processes can modify the ratio of its two stable isotopes δ37Cl (diffusion, ionic filtration, salt precipitation or phase change). To test this possibility, several types of experiments were performed to investigate the effects generated by a CO2 injection on Cl-isotopes. Autoclave experiments have shown that Cl can be solubilized in CO2SC, but the amounts would be too low to modify the isotopic signal of brines in case of any fractionation process. Reactive brine migration experiments by advection (ICARE1 percolation apparatus in Montpellier University) and diffusion (diffusion cell developed at IFPEN) were also conducted. No δ37Cl was observed during percolation (conservative advective transport) and the effects of diffusion remain to be investigated with regard to the evolution of rock porosity and permeability. Drying and salt precipitation experiments on porous media have shown that Cl concentrations and δ37Cl values can give information about transport processes during water evaporation. These experimental results allowed us to identify the processes capable of modifying the δ37Cl signal, and that Cl-isotopes can be of use for the monitoring of CO2 storage site