Mixed gas hydrate structures at the Chapopote Knoll, southern Gulf of Mexico

In underwater hydrocarbon seepage environments, gas hydrates are considered to play a significant role as shallow gas reservoirs and buffers for light hydrocarbon expulsion. Here we report on mixed hydrate structures from the Chapopote Knoll in the southern Gulf of Mexico and discuss several options on how a mixture of structure I (sI) and structure II (sII) gas hydrate may occur in nature. Locally resolving microscopic methods are needed to characterize the coexistence of different hydrate structures at geological hydrate deposits; we used Raman spectroscopy, X-ray diffraction, and gas chromatography for our investigations. Gas hydrates were found within the matrix and pores of the asphalts extruded at the seafloor. Two of the three hydrate pieces investigated comprised only sI, formed mostly from methane. In contrast, one piece comprised an intimate mixture of both sI and sII with sII representing ca. 25 wt.% and sI ca. 75 wt.% of the hydrate present. The two structures were closely associated within individual grain agglomerates. The crystallites of sII were significantly larger than of sI, suggesting differences in the nucleation density or different crystallite ages. The structural coexistence may be a result of one or more processes: i) de-mixing into two hydrate structures during the growth from the gas phase, which provides an additional degree of freedom for lowering the free energy in the system; ii) fractionated crystallization with a subsequently changing molecular composition; iii) crystallization from separated gas bubbles with different hydrocarbon compositions and water; and iv) partial transformation from sII to sI after hydrate nucleation, ceasing when a thermodynamically stable state was reached. The presented work will affect future assessments of natural hydrate deposits at thermogenic hydrocarbon systems, as it shows that both hydrate types I and II can be present at a certain geological site, and may provide a lingering strength to the system if conditions fall below the sI stability limit. This suggests that present worldwide hydrate occurrences are likely to be underestimated. (C) 2010 Elsevier B.V. All rights reserved.