(Table 1) Chemical composition of interstitial waters from the area of gas hydrate generation, Sea of Okhotsk

Distributions of halogens (Cl, Br and I) in interstitial waters from sediments containing methane hydrate and in water of the hydrate itself are presented. High concentrations of halogens do not occur in interstitial waters from sediments that contain gas hydrates. The main reason for their low concentrations is the poverty of organic matter in sediments.

(Table T1) Gas hydrate fabric and dipping angles of ODP Leg 204 sediments

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).

Organic carbon, calcium carbonate and carbon/nitrogen ratio at DSDP Leg 93 sites

A large number of samples of nonlithified and lithified sediments from Leg 93 sites were analyzed for their contents of organic carbon and calcium carbonate. An average of two samples was selected from every core for carbonate determination; organic carbon was measured in most of these samples. Nearly all of these analyses were performed on board Glomar Challenger for samples from Sites 603 and 604. Site 605 samples, plus some of the deeper samples from Hole 603B, were analyzed at the University of Michigan. The procedures used in both cases were virtually the same, and their results compared well. Organic carbon analyses were done using a Hewlett- Packard 185-B CHN Analyzer. Portions of samples selected for calcium carbonate determinations were treated with dilute HC1 to remove carbonate, washed with deionized water, and dried at 110°C. A Cahn Electrobalance was used to weight 20-mg samples of sediment for CHN analysis. Samples were combusted at 1050°C in the presence of an oxidant, and the volumes of the evolved gases determined as measures of the C, H, and N contents of sediment organic matter. Areas of gas peaks were determined and compared to those of rock standards of known carbon and nitrogen contents. These values were used to standardize instrument response so that C/N atomic ratios could be reported. Organic carbon concentrations were calculated on the basis of sediment dry weight. Hydrogen elemental analysis with the procedure used is untrustworthy because of the variable amounts of clay minerals and their hydrates, hence hydrogen values are not reported for samples analyzed by this method.

Degradation of [14C]GlcDGD in the marine sediment by monitoring radioactivity in the aqueous and gas phase using liquid scintillation counting (LSC) techniques

An experiment was conceived in which we monitored degradation of GlcDGD. Independent of the fate of the [14C]glucosyl headgroup after hydrolysis from the glycerol backbone, the 14C enters the aqueous or gas phase whereas the intact lipid is insoluble and remains in the sediment phase. Total degradation of GlcDGD then is obtained by combining the increase of radioactivity in the aqueous and gaseous phases. We chose two different sediment to perform this experiment. One is from microbially actie surface sediment sampled in February 2010 from the upper tidal flat of the German Wadden Sea near Wremen (53° 38' 0N, 8° 29' 30E). The other one is deep subsurface sediments recovered from northern Cascadia Margin during Integrated Ocean Drilling Program Expedition 311 [site U1326, 138.2 meters below seafloor (mbsf), in situ temperature 20 °C, water depth 1,828 m. We performed both alive and killed control experiments for comparison. Surface and subsurface sediment slurry were incubated in the dark at in situ temperature, 4 °C and 20 °C for 300 d, respectively. The sterilized slurry was stored at 20 °C. All incubations were carried out under N2 headspace to ensure anaerobic conditions. The sampling frequency was high during the first half-month, i.e., after 1, 2, 7, and 14 d; thereafter, the sediment slurry was sampled every 2 months. At each time point, samples were taken in triplicate for radioactivity measurements. After 300 d of incubation, no significant changes of radioactivity in the aqueous phase were detected. This may be the result of either the rapid turnover of released [14C] glucose or the relatively high limit of detection caused by the slight solubility (equivalent to 2% of initial radioactivity) of GlcDGD in water. Therefore, total degradation of GlcDGD in the dataset was calculated by combining radioactivity of DIC, CH4, and CO2, leading to a minimum estimate.

(Table 2) Methane to ethane ratio, and d13C-methane at DSDP Hole 76-533

Natural gas hydrates are clathrates in which water molecules form a crystalline framework that includes and is stabilized by natural gas (mainly methane) at appropriate conditions of high pressures and low temperatures. The conditions for the formation of gas hydrates are met within continental margin sediments below water depths greater than about 500 m where the supply of methane is sufficient to stabilize the gas hydrate. Observations on DSDP Leg 11 suggested the presence of gas hydrates in sediments of the Blake Outer Ridge. Leg 76 coring and sampling confirms that, indeed, gas hydrates are present there. Geochemical evidence for gas hydrates in sediment of the Blake Outer Ridge includes (1) high concentrations of methane, (2) a sediment sample with thin, matlike layers of white crystals that released a volume of gas twenty times greater than its volume of pore fluid, (3) a molecular distribution of hydrocarbon gases that excluded hydrocarbons larger than isobutane, (4) results from pressure core barrel experiments, and (5) pore-fluid chemistry. The molecular composition of the hydrocarbons in these gas hydrates and the isotopic composition of the methane indicate that the gas is derived mainly from microbiological processes operating on the organic matter within the sediment. Although gas hydrates apparently are widespread on the Blake Outer Ridge, they probably are not of great economic significance as a potential, unconventional, energy resource or as an impermeable cap for trapping upwardly migrating gas at Site 533.

Iodine ages of pore water at Hydrate Ridge, Cascadian continental margin

Hydrate Ridge off the coast of Oregon, USA, is a prime example for gas hydrate occurrences in active margin settings. It is part of the Cascadia Margin and was the focus of Ocean Drilling Program (ODP) Leg 204, which successfully recovered fluids from nine sites from the southern part of the ridge. Iodide concentrations in pore fluids associated with gas hydrates are strongly enhanced, by factors up to 5000 compared to seawater, which allows the use of this biophilic element as tracer for organic source regions. We applied the cosmogenic isotope 129I (T1/2=15.7 Ma) system to determine the age of the organic source formation responsible for the iodide enrichment. In all sites at ODP Leg 204, 129I/I ratios were found to decrease with depth to values around 250x10**-15, corresponding to minimum ages of 40 Ma, but in several sites, maxima in the 129I/I ratios point to the local addition of young iodide. The results indicate that a large amount of iodide was derived from deep accreted sediments of Eocene age, and that additional source regions provide iodide of Late Miocene age. The presence of old iodide in the pore waters suggests that fluid pathways are open to allow transport over large distances into the gas hydrate fields. The strong correlation between iodide and methane in hydrate fields coupled with the similarity in transport parameters in aqueous solutions suggests that a large fraction of methane in gas hydrates also has old sources and is transported into the present locations from source regions of Eocene age.

(Table 1) Grain size results, statistical parameters and magnetic susceptibility values of disturbed sediments from ODP holes 204-1249C and 204-1245B

Soupy and mousse-like fabrics are disturbance sedimentary features that result from the dissociation of gas hydrate, a process that releases water. During the core retrieval process, soupy and mousse-like fabrics are produced in the gas hydrate-bearing sediments due to changes in pressure and temperature conditions. Therefore, the identification of soupy and mousse-like fabrics can be used as a proxy for the presence of gas hydrate in addition to other evidence, such as pore water freshening or anomalously cool temperature. We present here grain-size results, mineralogical composition and magnetic susceptibility data of soupy and mousse-like samples from the southern Hydrate Ridge (Cascadia accretionary complex) acquired during Leg 204 of the Ocean Drilling Program. In order to study the relationship between sedimentary texture and the presence of gas hydrates, we have compared these results with the main textural and compositional data available from the same area. Most of the disturbed analyzed samples from the summit and the western flank of southern Hydrate Ridge show a mean grain size coarser than the average mean grain size of the hemipelagic samples from the same area. The depositional features of the sediments are not recognised due to disturbance. However, their granulometric statistical parameters and distribution curves, and magnetic susceptibility logs indicate that they correspond to a turbidite facies. These results suggest that gas hydrates in the southern Hydrate Ridge could form preferentially in coarser grain-size layers that could act as conduits feeding gas from below the BSR. Two samples from the uppermost metres near the seafloor at the summit of the southern Hydrate Ridge show a finer mean grain-size value than the average of hemipelagic samples. They were located where the highest amount of gas hydrates was detected, suggesting that in this area the availability of methane gas was high enough to generate gas hydrates, even within low-permeability layers. The mineralogical composition of the soupy and mousse-like sediments does not show any specific characteristic with respect to the other samples from the southern Hydrate Ridge.

Magnetic susceptibility parameters of ODP Leg 204 sites

In this paper, we present a rock magnetic data set produced for sediments from Hydrate Ridge recovered during Ocean Drilling Program Leg 204. Our data set is based on several artificially induced magnetic properties that can be used as a diagnostic for the presence of magnetic iron sulfides. The occurrence of magnetic iron sulfides within the gas hydrate stability zone in locations where gas hydrates are present seems to confirm previous interpretations linking formation of such minerals with generation of gas hydrate. Magnetic iron sulfides are also found at positions deeper than the gas hydrate stability zone. We suggest that these positions, which include intervals located just below the bottom-simulating reflector and also at deeper positions, may mark the former presence of gas hydrates that have been later dissociated as the gas hydrate stability zone moved upward through time. Detailed characterization of the magnetic iron sulfide mineralogy and comparison with sedimentological and geochemical data will be attempted for better determining the significance of magnetic iron sulfides in Hydrate Ridge sediments and their possible applications in the study of gas hydrates.