[1] We report the field observation of hydrate deposits of different crystal structures in the same cores of a mud volcano in the Kukuy Canyon. We link those deposits to chemical fractionation during gas hydrate crystallization. Gas composition and crystallographic analyses of hydrate samples reveal involvement of two distinct gas source types in gas hydrate formation at present or in the past: microbial (methane) and thermogenic (methane and ethane) gas types. The clathrate structure II, observed for the first time in fresh water sediments, is believed to be formed by higher mixing of thermogenic gas. Citation: Kida, M., et al. (2006), Coexistence of structure I and II gas hydrates in Lake Baikal suggesting gas sources from microbial and thermogenic origin,

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Isotopic fractionation of carbon and hydrogen in methane and ethane during the formation of gas hydrates was investigated. The gas hydrate samples were experimentally prepared in a pressure cell and isotopic compositions of both residual and hydrate‐bound gases were measured. δD of hydrate‐bound molecules of methane and ethane hydrates was several per mil lower than that of residual gas molecules in the formation processes, while there was no difference in the case of δ13C. These isotopic differences in δD are enough small for discussing the source types of hydrate‐bound gases using the δ13C‐δD diagram of Whiticar et al. [1986]. These results may provide useful insight into the formation process of gas hydrates.

To understand host-guest interactions of hydrocarbon clathrate hydrates, we investigated the crystal structure of simple and binary clathrate hydrates including butane (n-C4 H10 or iso-C4 H10 ) as the guest. Powder X-ray diffraction (PXRD) analysis using the information on the conformation of C4 H10 molecules obtained by molecular dynamics (MD) simulations was performed. It was shown that the guest n-C4 H10 molecule tends to change to the gauche conformation within host water cages. Any distortion of the large 5(12) 6(4) cage and empty 5(12) cage for the simple iso-C4 H10 hydrate was not detected, and it was revealed that dynamic disorder of iso-C4 H10 and gauche-nC4 H10 were spherically extended within the large 5(12) 6(4) cages. It was indicated that structural isomers of hydrocarbon molecules with different van der Waals diameters are enclathrated within water cages in the same way owing to conformational change and dynamic disorder of the molecules. Furthermore, these results show that the method reported herein is applicable to structure analysis of other host-guest materials including guest molecules that could change molecular conformations.

Pore-space gas hydrates sampled from the eastern Nankai Trough area off of Japan were minutely characterized using several instrumental techniques. Gas chromatographic results indicated that the natural gas in the sediment samples studied comprises mainly CH4. The concentrations of minor components varied according to depth. The powder X-ray diffraction patterns showed that the pore-space hydrates were of structure I (sI); the lattice constants were 1.183−1.207 nm. Both 13C NMR and Raman spectra confirmed that CH4 molecules were encaged in sI hydrate lattice. The average cage occupancies were calculated, respectively, from the Raman data as 0.83 for small cages and 0.97 for large cages. The hydration numbers were determined as 6.1−6.2.