(Table 1) Crystal sizes of measured samples from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon

The grain sizes of gas hydrate crystallites are largely unknown in natural samples. Single grains are hardly detectable with electron or optical microscopy. For the first time, we have used high-energy synchrotron diffraction to determine grain sizes of six natural gas hydrates retrieved from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon from varying depth between 1 and 101 metres below seafloor. High-energy synchrotron radiation provides high photon fluxes as well as high penetration depth and thus allows for investigation of bulk sediment samples. Gas hydrate grain sizes were measured at the Beam Line BW 5 at the HASYLAB/Hamburg. A 'moving area detector method', originally developed for material science applications, was used to obtain both spatial and orientation information about gas hydrate grains within the sample. The gas hydrate crystal sizes appeared to be (log-)normally distributed in the natural samples. All mean grain sizes lay in the range from 300 to 600 µm with a tendency for bigger grains to occur in greater depth. Laboratory-produced methane hydrate, aged for 3 weeks, showed half a log-normal curve with a mean grain size value of c. 40 µm. The grains appeared to be globular shaped.

Petrography, minerals and isotopic composition at DSDP Leg 66 Holes

We collected 20 carbonate nodules from the inner trench slope deposits of the Middle America Trench area off Mexico. Carbonate nodules are found only within the methane-rich layer beneath the mixed layer of methane and hydrogen sulfide. They have been investigated by microscopic, scanning electron microscopic (SEM), X-ray diffraction, and stable isotopic analytical methods. Calcite, magnesian calcite, dolomite, and rhodochrosite were recognized as carbonate minerals. Each carbonate nodule is usually represented by single species of carbonate minerals. Carbonate nodules are subdivided into micrite nodules and recrystallized nodules according to textural features. The carbonate crystallites in each micrite nodule are equidimensional. Their sizes range from several to 30 µm, as revealed by SEM micrographs. The chemical composition of calcite is changed from pure calcite to high magnesian calcite, as shown by the shift of the (104) reflection in X-ray diffraction patterns. Fe substitution for Ca in dolomite was also observed. Carbon isotopic composition shows an unusually wide range - from -42.9 to +13.5 per mil - in PDB scale, whereas oxygen isotopic compositions of almost all the carbonate nodules are constantly enriched in 18O from +3.4 to +7.60 per mil in PDB scale. These wide variations in carbon isotopic composition indicate several sources for the carbon in carbonate nodules. Carbon with a negative d13C value was derived from biochemical oxidation of methane with a negative d13C value. On the other hand, carbon with positive d13C value was probably formed during methane production in an anoxic condition.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

X-ray diffraction analysis, binocular component analysis and radiocarbon dating of sediment cores from the NW Iberian shelf system

Based on a well-established stratigraphic framework and 47 AMS-14C dated sediment cores, the distribution of facies types on the NW Iberian margin is analysed in response to the last deglacial sea-level rise, thus providing a case study on the sedimentary evolution of a high-energy, low-accumulation shelf system. Altogether, four main types of sedimentary facies are defined. (1) A gravel-dominated facies occurs mostly as time-transgressive ravinement beds, which initially developed as shoreface and storm deposits in shallow waters on the outer shelf during the last sea-level lowstand; (2) A widespread, time-transgressive mixed siliceous/biogenic-carbonaceous sand facies indicates areas of moderate hydrodynamic regimes, high contribution of reworked shelf material, and fluvial supply to the shelf; (3) A glaucony-containing sand facies in a stationary position on the outer shelf formed mostly during the last-glacial sea-level rise by reworking of older deposits as well as authigenic mineral formation; and (4) A mud facies is mostly restricted to confined Holocene fine-grained depocentres, which are located in mid-shelf position. The observed spatial and temporal distribution of these facies types on the high-energy, low-accumulation NW Iberian shelf was essentially controlled by the local interplay of sediment supply, shelf morphology, and strength of the hydrodynamic system. These patterns are in contrast to high-accumulation systems where extensive sediment supply is the dominant factor on the facies distribution. This study emphasises the importance of large-scale erosion and material recycling on the sedimentary buildup during the deglacial drowning of the shelf. The presence of a homogenous and up to 15-m thick transgressive cover above a lag horizon contradicts the common assumption of sparse and laterally confined sediment accumulation on high-energy shelf systems during deglacial sea-level rise. In contrast to this extensive sand cover, laterally very confined and maximal 4-m thin mud depocentres developed during the Holocene sea-level highstand. This restricted formation of fine-grained depocentres was related to the combination of: (1) frequently occurring high-energy hydrodynamic conditions; (2) low overall terrigenous input by the adjacent rivers; and (3) the large distance of the Galicia Mud Belt to its main sediment supplier.