Raman spectroscopic measurements of synthetic gas hydrates in the ocean

A Raman spectrometer extensively modified for deep ocean use was used to measure synthetic hydrates formed in an ocean environment. This was the first time hydrates formed in the ocean have been measured in situ using Raman spectroscopy. Gas hydrates were formed in situ in the Monterey Bay by pressurizing a Pyrex cell with various gas mixtures. Raman spectra were obtained for sI methane hydrate and sII methane + ethane hydrate. Gas occlusion resulting from rapid gas growth of methane hydrate was measured immediately after formation. The Raman shift for methane free gas was coincident with that of methane in the small 512 hydrate cage. The methane Raman peak widths were used to discriminate between methane in the free gas and hydrate phase. Methane + ethane sII hydrate was formed for 43 days on the seafloor. In this case, gas occlusion was not measured when the gas hydrates were allowed to form over an extended time period. Equivalent Raman spectra were obtained for the in situ and laboratory-formed sII methane + ethane hydrates, under similar p, T, and x conditions. With the Raman spectrometer operating in the ocean, seawater contributes to the Raman spectra obtained. Both the Raman bands for the sulfate ion and water were used to qualitatively determine the distribution of water phases measured (hydrate, seawater) in the Raman spectra.