Iodine is a biophilic element with one natural long-lived isotope, 129I (t1/2= 15.6 million years), and one stable isotope, 127I. The inventory of 129I in surface environments has been overwhelmed by anthropogenic releases over the past 50 years. The objective of this study is to utilize the elevated concentration and biophilic nature of 129I and the isotopic ratio of iodine (129I/127I) as a tracer of water mass movement and organic matter. Additionally, the significantly elevated values of 129I/127I could provide a geochronometer, similar to the way 14C is used, particularly for terrestrial organic matter that is less than 50 years old. A series of laboratory experiments and field investigations were carried out to characterize the dominant chemical forms of dissolved iodine, i.e., iodide (I-), iodate (IO 3-), and organic iodine (DOI) in natural waters. Sensitive methods were developed for the analysis of nanomolar quantities of 127I species in a variety of environmental systems using high performance liquid chromatography (HPLC) and an organic iodine decomposition technique, dehydrohalogenation. The potential use of 129I/127I as a hydrological tracer was evaluated through measurements of 129I and 127I, which were carried out in wells in the artificially recharged ground water basin of Orange County, California. Literature values of aquifer ages based on 3H/3He and δ18O tracer data, as well as time-series data of chloride and Santa Ana River flow rates over the past decade were compared to values for 129I and 127I. The iodine isotopes demonstrated a conservative behavior in these aquifers, suggesting that the observed variations of these isotopes reflect past river flow conditions during the time of recharge. The feasibility of using 129I/127I ratios to trace terrestrial organic matter across an estuary was tested. A novel analytical technique to determine 129I/127I ratios in DOI was developed for this investigation. The results of a Galveston Bay transect clearly show that 129I/127I ratios in DOI can remain elevated up to salinity of about 15, but that 129I/127I values of inorganic iodine species do not show any trend with change in salinity gradient due to fast isotopic and chemical equilibration in the estuarine waters.

Iodine is a biophilic element with one natural long-lived isotope, 129I (t1/2= 15.6 million years), and one stable isotope, 127I. The inventory of 129I in surface environments has been overwhelmed by anthropogenic releases over the past 50 years. The objective of this study is to utilize the elevated concentration and biophilic nature of 129I and the isotopic ratio of iodine (129I/127I) as a tracer of water mass movement and organic matter. Additionally, the significantly elevated values of 129I/127I could provide a geochronometer, similar to the way 14C is used, particularly for terrestrial organic matter that is less than 50 years old. A series of laboratory experiments and field investigations were carried out to characterize the dominant chemical forms of dissolved iodine, i.e., iodide (I-), iodate (IO 3-), and organic iodine (DOI) in natural waters. Sensitive methods were developed for the analysis of nanomolar quantities of 127I species in a variety of environmental systems using high performance liquid chromatography (HPLC) and an organic iodine decomposition technique, dehydrohalogenation. The potential use of 129I/127I as a hydrological tracer was evaluated through measurements of 129I and 127I, which were carried out in wells in the artificially recharged ground water basin of Orange County, California. Literature values of aquifer ages based on 3H/3He and δ18O tracer data, as well as time-series data of chloride and Santa Ana River flow rates over the past decade were compared to values for 129I and 127I. The iodine isotopes demonstrated a conservative behavior in these aquifers, suggesting that the observed variations of these isotopes reflect past river flow conditions during the time of recharge. The feasibility of using 129I/127I ratios to trace terrestrial organic matter across an estuary was tested. A novel analytical technique to determine 129I/127I ratios in DOI was developed for this investigation. The results of a Galveston Bay transect clearly show that 129I/127I ratios in DOI can remain elevated up to salinity of about 15, but that 129I/127I values of inorganic iodine species do not show any trend with change in salinity gradient due to fast isotopic and chemical equilibration in the estuarine waters.

La détermination de la concentration des RadioNucléides à Vie Longue (RNVL) dans les déchets de l'industrie nucléaire est essentielle pour la gestion sur le long terme des sites de stockages. Cette étude se focalise sur la détermination de la concentration de trois RNVL : 129I, 41Ca et 10Be dans les résines échangeuses d'ions utilisées pour la purification du fluide primaire des Réacteurs à Eau Pressurisée (REP). Afin d'exploiter les potentialités de la Spectrométrie de Masse par Accélérateur (SMA) pour mesurer ces radionucléides présents en de très faibles concentrations, des procédures analytiques spécifiques ont été développées incluant : 1) la minéralisation des échantillons, 2) l'extraction sélective des analytes, 3) le conditionnement pour la mesure par SMA. Appliquées à des échantillons de résines usées provenant d'une centrale EDF (REP 900 MWe), les procédures développées ont permis l'extraction quantitative et sélective des RNVL d'intérêt vis-à-vis des émetteurs β-γ et des isobares avant leur mesure par SMA sur l'instrument national ASTER (CEREGE, Aix-en-Provence). L'iode 129, le calcium 41 et le béryllium 10 ont été mesurés dans les résines usées à des concentrations de l'ordre de 10 ng/g, 20 pg/g et 4 ng/g de résine sèche, respectivement. Pour ce qui concerne l'iode 129 et le calcium 41, ces concentrations sont en accord avec celles estimées à partir de facteurs de corrélation établis relativement à des émetteurs gamma facilement mesurables (137Cs et 60Co). Dans le cas du béryllium 10, les résultats obtenus différent significativement des valeurs attendues mais sont cohérents avec de précédentes mesures réalisées par ICP-MS. / Determining the concentration of Long-Lived RadioNuclides (LLRN) in nuclear waste is fundamental for the long term management of storage sites. This study focuses on the determination of three LLRN concentrations, i.e. 129I, 41Ca and 10Be, in ion exchange resins used for primary fluid purification in Pressurized Water Reactors (PWR). To benefit from the Accelerator Mass Spectrometry (AMS) technique allowing to measure extremely low levels of nuclide concentrations, analytical procedures including: 1) sample dissolution; 2) selective and quantitative extraction of the analyte; and, 3) analyte conditioning for AMS measurements, were developed. Applied on spent resin samples collected at a 900 MW PWR, the procedures developed for each studied LLRN allowed their quantitative recovery and their selective extraction from β-γ emitters and isobars. The concentration measurements of the LLRN of interest were then performed on the Accelerator Mass Spectrometry national facility ASTER housed by the Centre Européen de Recherche et d'Enseignement des Géosciences de l'Environnement (CEREGE, Aix-en-Provence). 129I, 41Ca and 10Be concentrations in spent resins were measured to be about 10 ng/g, 20 pg/g and 4 ng/g of dry resin, respectively. Considering 129I and 41Ca, the measured concentrations agree with those assessed from scaling factors established relatively to easily measured gamma emitters (137Cs and 60Co). For 10Be, the presented results are significantly different from expected values but are in agreement with previous ICP-MS results.

The first comprehensive analysis of surface waters in the Labrador Sea for 236U was completed via Accelerator Mass Spectrometry. Through the analysis of 236U the method for AMS measurement was fine-tuned to allow for more precise results. Surface samples for the anthropogenic isotopes 137Cs and 129I were also collected along with two depth profiles of 129I. Samples were also collected in the Beaufort Sea and analyzed for the aforementioned isotopes. It was found that anthropogenic 129I from reprocessing plants is easily discernible at different concentrations among water bodies in both the Labrador and Beaufort Sea. 137Cs in surface waters is close to global fallout levels with no discernable influence from reprocessing plant inputs, but follows a similar trend to that of 129I with depth in the Beaufort Sea. 236U among surface waters in the Labrador Sea did not follow the same trends as 129I but had concentrations indicative of a mix of global fallout as well as reprocessing plant influenced waters. 236U samples from the Beaufort Sea were contaminated by an unknown source of 236U and were inconclusive but were reproducible and allowed for continued development of the AMS analysis methodology.

Huge amounts of anthropogenic 129I have been and still are released to the environment through liquid and gaseous discharges from the nuclear fuel reprocessing facilities worldwide and in particular the ones in Europe. Most of this 129I signal has been accumulated in the marine environment which plays a major role in the iodine natural pool.  In this thesis, an overview of available 129I concentrations in waters of the oceans and marginal seas together with new data about 129I and 127I spatial distribution in surface seawater along a transect between the North Sea and the northeastern Atlantic Ocean are presented. After comprehensive chemical separation, the concentrations of iodine isotopes (127I and 129I) and their species (iodide and iodate) were analysed using accelerator mass spectrometry and inductively-coupled plasma mass spectrometry. The results show that, generally, changes in the 127I and 127I-/127IO3- are comparable to data from other marine waters which are related to natural distribution patterns. A considerable variation of 129I along the transect is observed with the highest values occurring in the eastern English Channel and relatively low values obtained in the northeastern Atlantic Ocean. Inventory estimations of 129I in the North Sea and the English Channel are 147 kg and 78 kg, respectively, where more than 90% resides in the Southern Bight and the eastern English Channel. Iodate is the dominant iodine species for both 127I and 129I in most seawater samples from the North Sea to the Atlantic Ocean. 129I species variability suggests a slow process of 129I- oxidation in the open sea. It takes at least 10 years for the 129I-/129IO3- pair to reach their natural equilibrium as the water is transported from the English Channel. The results suggest a main transport of 129I from the western English Channel via the Biscay Bay into the northeastern Atlantic Ocean. Further, high 129I/127I and distinctive 129I-/129IO3- values south of 40°N indicate possible contribution of 129I through Mediterranean Outflow Water. The environmental radioactive impact of 129I and possible applications in ecosystem studies are also discussed.

129I is a radioactive isotope (T1/2= 15.7 million years) produced through natural and anthropogenic pathways, but the anthropogenic production is presently dominating the Earth’s surface environments. Sparse data from previous investigations in the Baltic Sea clearly indicated the occurrence of 129I at levels 3-4 orders higher than natural pre-atomic era (before 1940) without comprehensive evaluation of distribution and inventory. In this thesis extensive data on the distribution and inventory of iodine isotopes, 129I and 127I, and their species in waters of the Baltic Sea, Kattegat and Skagerrak are presented and used for estimation of water masses exchange and impact on the environment.  To fulfill these objectives seawater samples were collected in August 2006 and April 2007 in the Baltic Proper, Kattegat and Skagerrak as well as in December 2009 in the Bothnian Sea. After elaborative chemical separation of total iodine and iodine species, the analysis was performed using ICP-MS for 127I and AMS for 129I. The results reveal considerable differences in 129I concentration in terms of spatial and temporal variability and expose relatively high concentrations in the deep waters. Inventory estimates show higher amounts of 129I in August 2006 (24.2 ±15.4 kg) than in April 2007 (14.4± 8.3 kg) within the southern and central Baltic Proper, whereas almost a constant inventory is found in the Kattegat Basin. Relatively high 127I-/127IO3- and 129I-/129IO3- values in water of the Baltic Proper suggest effective reduction of iodate at a maximum rate of  8×10-7 (127IO3-) and 6×10-14 (129IO3-) (g/m3.day). The combination of 129I and 127I as tracers of water circulation in the Baltic Sea suggest that upwelling deep basinal water occurs into the surface along the Gotland deep and intrusion of North Atlantic water into southern Baltic. Furthermore, 129I-based model inventory reveals inflow of 330 km3/y (230-450 km3/y) water from the Kattegat into the Baltic Proper. Water exchange between the Baltic Proper and the Bothnian Sea and vice versa is estimated at 980 km3/y (600-1400 km3/y) and 1180 km3/y (780-1600 km3/y) respectively. Finally, an environmental assessment of radioactivity associated with 129I burden in the Baltic Sea region is discussed.

Un pic de 60Fe récemment observé dans une croûte ferromanganésienne a été interprété comme la trace de l'explosion d'une supernova qui aurait explosé, suffisamment proche du système solaire pour qu'elle puisse y déposer son empreinte sur la Terre, il y a 2.8 ° 0.4 millions d'années (Myr). Pour confirmer cette interprétation, d'une part avec une meilleure résolution temporelle, d'autre part en ayant accès à la mesure simultanée d'autres isotopes dans différentes phases géochimiques, les sédiments marins sont un outil particulièrement adapté. Ce travail a pour objectif de rechercher dans les sédiments marins les résidus de cette supernova sous forme d'anomalies isotopiques. Les trois principaux noyaux auxquels nous nous sommes intéressés sont l'129I, le 60Fe, et l'26Al, tous trois mesurés sous forme de rapports isotopiques par Spectrométrie de Masse par Accélérateur (SMA). Quantifier le flux des noyaux correspondant à la signature de cette supernova permettrait de mieux contraindre les modèles théoriques de nucléosynthèse stellaire. Ces résidus sont des isotopes produits par une séquence de combustions hydrostatiques pendant l'évolution stellaire et/ou par nucléosynthèse explosive lors de l'explosion de la supernova. Les conditions qui règnent au moment de l'explosion (température, densité de neutrons) permettent de penser que les supernovae pourraient être le site astrophysique du processus r.<br />L'étude en 129I a montré que la mesure de rapports 129I/127I pré-anthropogéniques nécessite un contrôle très strict des différentes sources possibles de contaminations en 129I, et ce d'autant plus lorsque l'on travaille avec de petites quantités d'iode (quelques microgrammes). Cette étude a permis de révéler un écart de plusieurs ordres de grandeurs entre la valeur pré-anthropogénique théorique et expérimentale du rapport 129I/127I dans le milieu marin. Les mesures SMA en 60Fe et 26Al ont permis d'établir, dans la phase authigène des sédiments marins, l'absence de signal en 60Fe sur la zone temporelle correspondant au signal observé dans la croûte Fe-Mn (2.4-3.2 Myr), ainsi qu'en 26Al de 2.6 à 3.2 Myr.