Unraveling the Role of Natural Sediments in sII Mixed Gas Hydrate Formation: An Experimental Study.

Considering the ever-increasing interests in natural gas hydrates, a better and more precise knowledge of how host sediments interact with hydrates and affect the formation process is crucial. Yet less is reported for the effects of sediments on structure II hydrate formation with complex guest compositions. In this study, experimental simulations were performed based on the natural reservoir in Qilian Mountain permafrost in China (QMP) due to its unique properties. Mixed gas hydrates containing CH4, C2H6, C3H8, and CO2 were synthesized with the presence of natural sediments from QMP, with quartz sands, and without sediments under identical p-T conditions. The promoting effects of sediments regardless of the grain size and species were confirmed on hydrate formation kinetics. The ice-to-hydrate conversion rate with quartz sand and natural QMP sediments increased by 23.5% and 32.7%, respectively. The compositions of the initial hydrate phase varied, but the difference became smaller in the resulting hydrate phases, having reached a steady state. Beside the structure II hydrate phase, another coexisting solid phase, neither ice nor structure I hydrate, was observed in the system with QMP sediments, which was inferred as an amorphous hydrate phase. These findings are essential to understand the mixed gas hydrates in QMP and may shed light on other natural hydrate reservoirs with complex gas compositions.

Influence of Gas Supply Changes on the Formation Process of Complex Mixed Gas Hydrates.

Natural gas hydrate occurrences contain predominantly methane; however, there are increasing reports of complex mixed gas hydrates and coexisting hydrate phases. Changes in the feed gas composition due to the preferred incorporation of certain components into the hydrate phase and an inadequate gas supply is often assumed to be the cause of coexisting hydrate phases. This could also be the case for the gas hydrate system in Qilian Mountain permafrost (QMP), which is mainly controlled by pores and fractures with complex gas compositions. This study is dedicated to the experimental investigations on the formation process of mixed gas hydrates based on the reservoir conditions in QMP. Hydrates were synthesized from water and a gas mixture under different gas supply conditions to study the effects on the hydrate formation process. In situ Raman spectroscopic measurements and microscopic observations were applied to record changes in both gas and hydrate phase over the whole formation process. The results demonstrated the effects of gas flow on the composition of the resulting hydrate phase, indicating a competitive enclathration of guest molecules into the hydrate lattice depending on their properties. Another observation was that despite significant changes in the gas composition, no coexisting hydrate phases were formed.

A new high-pressure cell for systematic in situ investigations of micro-scale processes in gas hydrates using confocal micro-Raman spectroscopy.

Natural gas hydrates are ice-like solids composed of gas and water molecules. They are found worldwide at all continental margins as well as in permafrost regions. Depending on the source of the enclathrated gas molecules, natural gas hydrates may occur as coexisting phases with different structures containing predominantly CH4, but also a variety of hydrocarbons, CO2 or H2S. For a better understanding of these complex hydrate formation processes on a micrometer level, an experimental setup with a new high-pressure cell was developed, which can be used in a pressure range between 0.1 MPa and 10.0 MPa. Peltier elements ensure precise cooling of the cell in a temperature range between 243 K and 300 K. The selected temperature and pressure ranges in which the cell can be used make it possible to simulate the formation of gas hydrates in their natural environment, e.g., on continental margins or in permafrost areas at a depth of up to 1000 m. The cell body is made of Hastelloy, which generally also allows the use of corrosive gases, such as H2S, in the experiments. The inner sample space has a volume of about 550 µl. A quartz window allows for microscopic observations and the systematic and continuous in situ Raman spectroscopic investigations of the forming hydrate phase mimicking natural conditions. Single point measurements, line scans, and area maps provide information on spatial heterogeneities regarding compositions and cage occupancies. The pressure cell can be operated as a closed system or as an open system with a defined continuous gas flow. The use of a continuous gas flow also allows for the in situ investigation of transformation processes induced by changes of the feed gas composition. In this paper, all details of the new experimental setup as well as preliminary results of our investigations on the formation of complex mixed hydrate systems both in the open and closed systems as well as the CH4-CO2 transformation process are presented.

Characteristics of Authigenic Minerals around the Sulfate-Methane Transition Zone in the Methane-Rich Sediments of the Northern South China Sea: Inorganic Geochemical Evidence.

Sediments at marine cold seep areas provide potential archives of past fluid flow, which allow insights into the evolution of past methane seepage activities. However, signals for anaerobic oxidation of methane (AOM) might be obscured in bulk sediments in cold-seep settings due to several factors, especially flood and turbidite deposition. Comprehensive inorganic data were gathered in this study to explore the availability of related records at cold seeps and to provide insights into the evolution of past methane seepage activities. Sediments collected from the site 973-4 in the Taixinan Basin on the northern slope of the South China Sea were characterized in terms of total carbon and sulfur, δ13C values of total organic carbon (δ13CTIC), δ34S values of chromium reducible sulfur (δ34SCRS), and foraminiferal oxygen and carbon isotopes. The results confirmed a strong correlation between formation of authigenic minerals and AOM. Moreover, the 34S enrichments and abundant chromium reducible sulfur (CRS) contents in the authigenic sulfides in the sulfate-methane transition zone (SMTZ) within 619-900 cm below seafloor (cmbsf) reflected past high methane fluxes supported by constant methane seepages. Lithological distribution and AMS (Accelerator Mass Spectra) 14C dating of planktonic foraminifera show that the turbidite (~35.14 ka) was related to a foraminifera-rich interval (Unit II: 440-619 cmbsf) and increased carbonate productivity during the last glacial maximum (LGM). Enrichment of Mo and U was observed accompanied by low contents of nutrient metals (Al, Ti, V, Ni, Fe, Mn, and Cu) in Unit II. The foraminifera-rich interval (Unit II) of cold seep sediments was probably linked to the phenomenon of inconsecutive sedimentary sequence due to the turbidites, which resulted in the lack of Fe, Mn, and Ba enrichment. There is no U enrichment but only Mo enrichment within Unit III, which might be related to H2S produced by AOM during the methane seepages. Based on the above results, it can be speculated that this area has experienced multiple-episodes of methane seep events. Further exploration of AOM should focus on the risks of rapid deposition, especially the impact of turbidity current on sediments.