Gas hydrate dissolution rates quantified with laboratory and seafloor experiments

Methane hydrates are stable at high pressure, low temperature, and saturated methane concentrations. However, natural hydrates exist at the seafloor where methane concentrations are well below saturation. Under such conditions, hydrate outcrops should shrink rapidly as they dissolve into the surrounding seawater. However, some natural hydrate outcrops have been observed for years undergoing little to no visible signs of change. Further, hydrate dissolution rates vary greatly among sites where changes have been observed. In this study, we perforated a natural hydrate outcrop on the seafloor of the Gulf of Mexico and measured the expansion of the hole after 30 days. From the rate of volume loss, we calculated a dissolution rate of 15 cm y(-1). This rate is nearly an order of magnitude slower than hydrate dissolution rates observed in the Northern Cascadia Margin. We hypothesized that crystal structure influences hydrate dissolution rates and that the variability observed in in situ hydrate dissolution is caused by different hydrate structures. To test this hypothesis, we measured methane hydrate (structure I) and propane hydrate (structure II) dissolution rates in a series of laboratory experiments. Hydrates were formed in a pressure vessel and maintained at pressure and temperature conditions conducive to hydrate stability. After formation, the gas source was removed. Dissolution rates were calculated by measuring the increase in the dissolved gas concentration over time. Structure I (methane) hydrate dissolved at an average rate of 5.2 +/- 2.5 mM CH4 d(-1). Structure II (propane) hydrate dissolved at an average rate of 0.3 +/- 0.2 mM C3H8 d(-1). The ratio of these dissolution rates was proportional to the ratio of methane and propane solubilities under the experimental conditions. This suggests that dissolution rates in our experiments were diffusion-controlled and not influenced by differences in the crystal structure. We propose that natural contaminants such as oils or biofilms may have slowed the dissolution rate of the hydrate we observed in the Gulf of Mexico. (C) 2013 Elsevier Ltd. All rights reserved.