Radiocarbon calibration is a fundamental stage of the radiocarbon dating process if meaningful calendar ages are to be derived from samples’ radiocarbon determinations. However, the present limit of direct, non-reservoir-corrected, atmospheric radiocarbon calibration is 12,550 calibrated years before present (Reimer et al. 2009), leaving approximately three quarters of the radiocarbon timescale to be necessarily calibrated via less secure marine records. The sediment profile of Lake Suigetsu, Honshu Island, central Japan, offers an ideal opportunity from which to derive an extended, ‘wholly terrestrial’ and continuous record of atmospheric radiocarbon back to the limits of radiocarbon detection (circa 60,000 years before present). The presence of well-defined, annually-deposited laminae (varves) throughout this extended time period provides an independent, high resolution chronometer against which radiocarbon measurements, performed upon plant macrofossil samples retrieved from the sediment column, can be directly related. This site was first exploited for radiocarbon calibration purposes by Kitagawa and van der Plicht (1998a, 1998b), however, issues pertaining to the reliability of the calendar age scale of this work precluded the widespread uptake of this dataset. The work presented in this DPhil thesis represents a significant contribution to the broader, ‘Suigetsu Varves 2006’ project – an international collaboration centring on the re-coring of Lake Suigetsu, which was undertaken in summer 2006 to improve upon the shortcomings of the previous project and, thereby, to fully exploit the site’s potential for both radiocarbon calibration and multi-proxy palaeoenvironmental study (Nakagawa et al. 2011). This DPhil thesis describes the generation of the revised (‘SG06’) terrestrial radiocarbon calibration dataset from Lake Suigetsu, comprising 647 accelerator mass spectrometry (AMS) radiocarbon determinations, and extending across the complete range of the radiocarbon dating method. Furthermore, visual matching of archive SG93 core sections to the continuous SG06 sediment profile was undertaken, allowing the integration of the ≈ 300 radiocarbon determinations from the original Lake Suigetsu project into a higher resolution (≈ 900 radiocarbon measurements), combined Lake Suigetsu radiocarbon calibration dataset, providing a unique reconstruction of atmospheric radiocarbon across the entire radiocarbon dating timescale.

Le géochronomètre Re-Os a fait ses preuves dans son application aux huiles et bitumes pétroliers. Cependant, l’application de ce système sur les fluides pétroliers souffre d’un manque de compréhension de la géochimie pétrolière de Re et Os, des mécanismes de remise à zéro du géochronomètre et par conséquent des évènements réellement datés. Plus précisément, l’utilisation du géochronomètre Re-Os nécessite de comprendre la manière dont le comportement du système Re-Os permet de remplir les conditions nécessaire au développement d’une isochrone. Ces conditions sont : 1) l’homogénéisation isotopique des huiles à l’échelle d’un champ pétrolier ; 2) le fractionnement de Re par rapport à Os pour obtenir des échantillons ayant différents rapport Re/Os ; 3) la fermeture du système jusqu’au moment de la datation. Des protocoles expérimentaux ont ainsi été mis au point afin de comprendre le comportement géochimique de Re et Os dans les huiles afin d’évaluer l’utilisation du système Re-Os en tant que géochronomètre dans le cadre d’une application directe sur les pétroles. Le fractionnement de Re et Os a été vérifié dans le cas de la perte d’asphaltènes au cours de l’évolution de l’huile par précipitation séquentielle en laboratoire. Des expériences de contact entre solutions aqueuses de Re et Os et huiles ont été conduites afin d’étudier la possibilité d’un transfert des métaux entre ces deux phases sur une large gamme de concentrations et de températures. Enfin, l’étude de spéciation de Re et Os dans les huiles artificiellement enrichies en Re et Os par spectroscopie d’absorption X (rayonnement synchrotron) a permis de proposer un mécanisme d’incorporation de Re et Os dans les huiles / The Re-Os radiogenic system is well adapted to the dating of oils and bitumen. However the meaning of the obtained age is ambiguous. This is mainly due to gaps in our knowledge of the geochemical behavior and the speciation of Re and Os in oils. Specifically, use of the Re-Os system requires an understanding of how Re-Os behavior can lead to the fulfillment of the conditions necessary for the development of an isochron. These conditions are: 1) the isotopic homogenization of oils at the scale of a petroleum field 2) the fractionation of Re from Os so as to obtain samples with various Re/Os ratios 3) the closure of the system during the period of radiogenic ingrowth of the daughter isotope, that is, from the time of the event of interest to the present day. Experimental investigation of the organic geochemical behavior of Re and Os in oils under various conditions, designed as analogs of the different stages of petroleum generation and evolution, were performed in order to evaluate the use of the Re-Os system as a geochronometer in the context of a direct use on petroleum. The possibility of Re-Os fractionation resulting from asphaltene loss during oil evolution was investigated by sequential asphaltene precipitation in the laboratory. The possibility of metal transfer from formation waters to petroleum was studied by performing contact experiments between oils and aqueous solutions of Re and Os of various concentrations over a wide range of temperatures and for varying periods of time. Finally, the study by X-ray absorption spectroscopy of Re and Os in oils artificially enriched in these elements contributed to the proposal of a mechanism for Re and Os incorporation at the oil-water interface