Gas hydrate formation in the deep sea: In situ experiments with controlled release of methane, natural gas, and carbon dioxide

We have utilized a remotely operated vehicle (ROV) to initiate a program of research into gas hydrate formation in the deep sea by controlled release of hydrocarbon gases and liquid CO₂ into natural sea water and marine sediments. Our objectives were to investigate the formation rates and growth patterns of gas hydrates in natural systems and to assess the geochemical stability of the reaction products over time. The novel experimental procedures used the carrying capacity, imaging capability, and control mechanisms of the ROV to transport gas cylinders to depth and to open valves selectively under desired P−T conditions to release the gas either into contained natural sea water or into sediments. In experiments in Monterey Bay, California, at 910 m depth and 3.9 °C water temperature we find hydrate formation to be nearly instantaneous for a variety of gases. In sediments the pattern of hydrate formation is dependent on the pore size, with flooding of the pore spaces in a coarse sand yielding a hydrate cemented mass, and gas channeling in a fine-grained mud creating a veined hydrate structure. In experiments with liquid CO₂ the released globules appeared to form a hydrate skin as they slowly rose in the apparatus. An initial attempt to leave the experimental material on the sea floor for an extended period was partially successful; we observed an apparent complete dissolution of the liquid CO₂ mass, and an apparent consolidation of the CH₄ hydrate, over a period of about 85 days.