Thesis (Ph. D.)--Joint Program in Marine Geology and Geophysics (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), September 2003. / Includes bibliographical references. / Groundwater discharge into estuaries and the coastal ocean is an important mechanism for the transport of dissolved chemical species to coastal waters. Because many dissolved species are present in groundwater in concentrations that are orders of magnitude higher than typical river concentrations, groundwater-borne nutrients and pollutants can have a substantial impact on the chemistry and biology of estuaries and the coastal ocean. However, direct fluxes of groundwater into the coastal ocean (submarine groundwater discharge, or SGD) can be difficult to quantify. Geochemical tracers of groundwater discharge can reflect the cumulative SGD flux from numerous small, widely dispersed, and perhaps ephemeral sources such as springs, seeps, and diffuse discharge. The natural radiocarbon content (A14C) of dissolved inorganic carbon (DIC) was developed as a tracer of fresh, terrestrially driven fluxes from confined aquifers. This A14C method was tested during five sampling periods from November 1999 to April 2002 in two small estuaries in southeastern North Carolina. In coastal North Carolina, fresh water artesian discharge is characterized by a low A14C signature acquired from the carbonate aquifer rock. Mixing models were used to evaluate the inputs from potential sources of DIC-A'4C to each estuary, including seawater, springs, fresh water stream inputs, and salt marsh respiration DIC additions. These calculations showed that artesian discharge dominated the total fresh water input to these estuaries during nearly all sampling periods. / (cont.) These new A14C-based SGD estimates were compared with groundwater flux estimates derived from radium isotopes and from radon-222. It is clear that these tracers reflect different components of the total SGD. The fluxes of low-A14C and of 222Rn were dominated by artesian discharge. Estuarine 226Ra showed strong artesian influence, but also reflected the salt water SGD processes that controlled the other three radium isotopes. The flux of 228Ra seemed to reflect seepage from the terrestrial surficial aquifer as well as salt water recirculation through estuarine sediments. The fluxes of 224Ra and 223Ra were dominated by salt water recirculation through salt marsh sediments. This multi-tracer approach provides a comprehensive assessment of the various components contributing to the total SGD. / by Carolyn M. Gramling. / Ph.D.

Une solution prometteuse pour diminuer les émissions anthropogéniques de gaz à effet de serre consiste à injecter une partie des rejets industriels de CO2 dans des formations souterraines. Celles-ci comportent un réservoir entouré de roches de couverture, qui constituent la première barrière à la migration des fluides. La caractérisation de leurs propriétés de confinement et de leur évolution en présence de CO2 est donc un élément clé de la sécurité d’un site de stockage. Le travail présenté propose une méthodologie, appliquée ici à des roches carbonatées du bassin parisien, permettant de mesurer les paramètres de transport de roches de couverture et les conséquences d’un vieillissement en conditions représentatives de celles d’un stockage en aquifère profond. La pression de percée, le coefficient de diffusion des produits de dissolution du CO2, et la perméabilité, paramètres contrôlant les principaux mécanismes de fuite, ont été mesurés avant et après altération des matériaux par réaction avec une saumure saturée en CO2 dans des conditions thermodynamiques typiques d’un réservoir (environ 80°C et 100 bar). Les résultats obtenus ont révélé un bon comportement global des roches, mais également une forte diminution du potentiel de confinement en présence de défauts structurels initiaux (fractures rebouchées, pores de grand diamètre...). Une simulation numérique décrivant les évolutions de la formation rocheuse non-fissurée sur une durée de 1000 ans a été réalisée en s’appuyant sur des paramètres mesurés directement ou obtenus par modélisation des essais d’altération. Elle a montré que les transformations engendrées par le stockage de CO2 sous une roche de couverture homogène restent très limitées spatialement / A promising solution to reduce anthropogenic emissions of greenhouse effect gases consists in the injection and long-term storage of a part of the industrial carbon dioxide discharges in underground formations. These formations must be composed of a reservoir surrounded by tight caprocks, which represent the first barrier preventing fluids migration. The characterization of their confining properties and of their evolution in presence of CO2 is thus a key element regarding a storage site security. This work presents a methodology allowing the measurement of caprocks transport parameters and the consequences of an alteration under representative conditions of deep aquifers storage. This methodology was applied to carbonate rocks from the Paris basin. The breakthrough pressure, the diffusion coefficient of CO2 dissolution products, and the permeability, controlling parameters of leakage mechanisms, were measured before and after alteration of the materials by reaction with a CO2-saturated brine under reservoir thermodynamic conditions (about 80°C and 100 bar). Results revealed a satisfactory global behaviour under these aggressive conditions, but also a strong diminution of the confinement potential in presence of initial structural faults (sealed fractures, large-diameter pores…) forming higher-permeability zones. A numeric simulation describing the evolution of a homogeneous rock formation during 1000 years was also realized based on parameters directly measured or obtained by modelling of the alteration experiments. It showed that the transformations brought by the CO2 storage under a rock formation with no initial faults remain very localized spatially