Gas Diffusion and Fractionation in Clathrated Ice-Core Samples (Abstract)

Abstract

The evolution of gas content from clathrated ice is very sensitive to pressure and to storage temperature. As such substances are likely to be found in deep Antarctic ice and the Greenland ice sheet (Miller 1969, Shoji and Langway 1982), the influence of clathrate formation and incomplete back-diffusion on the measured air composition was investigated.We have undertaken laboratory studies on the kinetics of formation and decomposition of clathrate hydrates of air and carbon dioxide. The kinetics were found to be controlled mainly by the self-diffusion of water molecules. The clathrate structure being of type II (Davidson and others 1984), the diffusion of guest molecules and the role of auxiliary gases was studied.A bubble-relaxation model is presented for air-hydrate inclusions in fresh ice cores. It takes into account the diffusion constant for desorption of clathrates and the mechanical relaxation of the bulk ice. The increasing pressure and the initially low bubble surface are factors which limit the rate of decomposition. The rate of decomposition was compared with the natural bubble relaxation measured in deep ice cores (Gow and Williamson 1975).Fractionation was also observed through the formation and decomposition of mixed hydrates. The diffusion control of the recrystallization process affects this fractionation.On the basis of this study we make some recommendations for the analysis of deep ice-core samples.