Description: Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct–Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg− 1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Description: The sediments of Hydrate Ridge/Cascadia margin contain extensive amounts of gas hydrate. A total of 57 sediment samples including gas hydrate were preserved in liquid nitrogen and have been imaged using computerized tomography to visualize hydrate distribution and shape. The analysis gives evidence that gas hydrate in vein and veinlet structures is the predominant shape in the deeper gas hydrate stability zone with dipping angles from 30° to 90°(vertical).

Description: Drilling on Hydrate Ridge, offshore Oregon, during ODP Leg 204 enabled us to investigate fabrics of gas hydrate samples in a wide depth range of the gas hydrate stability zone (GHSZ). X-ray computerized tomographic imaging on whole-round samples, frozen in liquid nitrogen, revealed that layered gas hydrate structures are related to variable processes occurring at different sediment depths. Shallow gas hydrates often form layers parallel or sub-parallel to bedding and also crosscut sedimentary strata and other gas hydrate layers, destroying the original depositional fabric. The dynamic processes interacting with this complicated plumbing system in this shallow environment are responsible for such highly variable gas hydrate fabrics. Gas hydrate layers deeper in the sediments are most often dipping with various angles, and are interpreted as gas hydrate precipitates filling tectonic fractures. These originally open fractures are potential candidates for free gas transportation, and might explain why free gas can rapidly emanate from below the bottom-simulating reflector through the GHSZ to the seafloor.

Description: Free or hydrate-bound gas in the seafloor has been of scientific, ecologic and economic interest for many years because it predominantly contains high concentrations of low-molecular-weight hydrocarbons. A prerequisite of accurate quantifications of gases in sediments is to preserve pressure and temperature close to the in situ conditions during recovery. Here we introduce two new sediment coring devices that allow for the recovery of near-surface gas- and gas-hydrate-bearing sediments and subsequent investigations using several different techniques such as visualisation by computerized tomography, quantitative degassing, and sediment and porewater analyses. The first coring tool, the Multiple Autoclave Corer (MAC), resembles a standard multiple corer in terms of applications, size and core length of about 55 cm. The second tool, the Dynamic Autoclave Piston Corer (DAPC), is similar to a piston corer in application and size and enables one to take cores of up to 2.5 m length. Both focus on the investigation of near-surface sediments, which are most strongly affected by changes in bottom-water temperature and hydrostatic pressure, which in turn influence continental slope stability. Some results from recent offshore applications show the potential of these tools.

Description: The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis (“Rietveld method”) of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.