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We present a theoretical study of the thermodynamic chemical equilibrium of gas hydrate in soil by taking into account the influence of temperature, pressure, pore water chemistry, and the mean pore size distribution. The model uses a new formulation based on the enthalpy form of the law of conservation of energy. The developed model shows that due to a temperature and pressure increase, hydrates may dissociate at the top of the hydrate occurrence zone to ensure a chemical equilibrium with the surrounding bulk water. This original result confirms what has been already shown through experiments. The second part of the paper presents an application of the model through a back-analysis of the giant Storegga Slide on the Norwegian margin. Two of the most important changes during and since the last deglaciation (hydrostatic pressure due to the change of the sea level and the increase of the sea water temperature) were considered in the calculation. Simulation results show that melting of gas hydrate due to the change of the gas solubility can be at the origin of a retrogressive failure initiated at the lower part of the Storegga slope. Once again, the developed model leads to predictions, which are supported by laboratory experiment results, but contradictory to previous interpretations and beliefs considering that hydrate dissociation occurs only at the bottom of the gas hydrate stability zone.

The assessment of climate change factors includes a constraint of methane sources and sinks. Although marine geological sources are recognized as significant, unfortunately, most submarine sources remain poorly quantified. Beside cold vents and coastal anoxic sediments, the large number of submarine mud volcanoes (SMV) may contribute significantly to the oceanic methane pool. Recent research suggests that methane primarily released diffusively from deep-sea SMVs is immediately oxidized and, thus, has little climatic impact. New hydro-acoustic, visual, and geochemical observations performed at the deep-sea mud volcano Håkon Mosby reveal the discharge of gas hydrate-coated methane bubbles and gas hydrate flakes forming huge methane plumes extending from the seabed in 1250 m depth up to 750 m high into the water column. This depth coincides with the upper limit of the temperature-pressure field of gas hydrate stability. Hydrographic evidence suggests bubble-induced upwelling within the plume and extending above the hydrate stability zone. Thus, we propose that a significant portion of the methane from discharged methane bubbles can reach the upper water column, which may be explained due to the formation of hydrate skins. As the water mass of the plume rises to shallow water depths, methane dissolved from hydrated bubbles may be transported towards the surface and released to the atmosphere. Repeated acoustic surveys performed in 2002 and 2003 suggest continuous methane emission to the ocean. From seafloor visual observations we estimated a gas flux of 0.2 (0.08-0.36) mol s−1 which translates to several hundred tons yr−1 under the assumption of a steady discharge. Besides, methane was observed to be released by diffusion from sediments as well as by focused outflow of methane-rich water. In contrast to the bubble discharge, emission rates of these two pathways are estimated to be in the range of several tons yr−1 and, thus, to be of minor importance. Very low water column methane oxidation rates derived from incubation experiments with tritiated methane suggest that methane is distributed by currents rather than oxidized rapidly.

From the Hå kon Mosby Mud Volcano (HMMV) on the southwest Barents Sea shelf, gas and fluids are expelled by active mud volcanism. We studied the mass transfer phenomena and microbial conversions in the surface layers using in situ microsensor measurements and on retrieved cores. The HMMV consists of three concentric habitats: a central area with gray mud, a surrounding area covered by white mats of big sulfide oxidizing filamentous bacteria (Beggiatoa), and a peripheral area colonized by symbiontic tube worms (Pogonophora). A fourth habitat comprised gray microbial mats near gas seeps. The differences between these four methane-fueled habitats are best explained by different transport rates of sulfate into the sediments and porewater upflow rates. The upflow velocities were estimated by two independent methods at 3-6 m yr 21 in the central area and 0.3-1 m yr 21 in Beggiatoa mats. In the central area no sulfide was found, indicating that the rapidly rising sulfate-free fluids caused sulfate limitation that inhibited anaerobic oxidation of methane (AOM). Under Beggiatoa mats a steep sulfide peak was found at 2 to 3 cm below the seafloor (bsf), most likely due to AOM. All sulfide was oxidized anaerobically, possibly through nitrate reduction by Beggiatoa. The Beggiatoa mats were dominated by a single filamentous morphotype with a diameter of 10 mm and abundant sulfur inclusions. A high diversity of sulfide oxidizer morphotypes was observed in a grayish microbial mat near gas vents, where aerobic sulfide oxidation was important. The sediments colonized by Pogonophora were influenced by bioventilation, allowing sulfate penetration and AOM to 70 cm bsf. The HMMV is a unique and diverse ecosystem, the structure and functioning of which is mainly controlled by pore-water flow.Interest in anaerobic oxidation of methane (AOM) and its linkage to sulfate reduction was strongly stimulated by the recent discovery of the microorganisms involved (Boetius et al. 2000;Michaelis et al. 2002;Orphan et al. 2002). Evidence was presented that consortia of methanotrophic archaea and sulfate-reducing bacteria are responsible for the process. These microorganisms were found in high abundance in methane-rich sediments above gas hydrates and various types of cold seeps. The microbial conversion of methane and sulfate to CO 2 and sulfide in surface sediments is usually accompanied by sulfide oxidation (SO) by free-living and symbiotic bacteria.1 Corresponding author (dbeer@mpi-bremen.de).

High-resolution seismic experiments, employing arrays of closely spaced, four-component ocean-bottom seismic recorders, were conducted at a site off western Svalbard and a site on the northern margin of the Storegga slide, off Norway to investigate how well seismic data can be used to determine the concentration of methane hydrate beneath the seabed. Data from P-waves and from S-waves generated by P-S conversion on reflection were inverted for P-and S-wave velocity (Vp and Vs), using 3D travel-time tomography, 2D ray-tracing inversion and 1D waveform inversion. At the NW Svalbard site, positive Vp anomalies above a sea-bottomsimulating reflector (BSR) indicate the presence of gas hydrate. A zone containing free gas up to 150-m thick, lying immediately beneath the BSR, is indicated by a large reduction in Vp without significant reduction in Vs. At the Storegga site, the lateral and vertical variation in Vp and Vs and the variation in amplitude and polarity of reflectors indicate a heterogeneous distribution of hydrate that is related to a stratigraphically mediated distribution of free gas beneath the BSR. Derivation of hydrate content from Vp and Vs was evaluated, using different models for how hydrate affects the seismic properties of the sediment host and different approaches for estimating the background velocity of the sediment host. The error in the average Vp of an interval of 20-m thickness is about 2.5%, at 95% confidence, and yields a resolution of hydrate concentration of about 3%, if hydrate forms a connected framework, or about 7%, if it is both pore-filling and framework-forming. At NW Svalbard, in a zone about 90-m thick above the BSR, a Biot-theory-based method predicts hydrate concentrations of up to 11% of pore space, and an effective-medium-based method predicts concentrations of up to 6%, if hydrate forms a connected framework, or 12%, if hydrate is both pore-filling and frameworkforming. At Storegga, hydrate concentrations of up to 10% or 20% were predicted, depending on the hydrate model, in a zone about 120-m thick above a BSR. With seismic techniques alone, we can only estimate with any confidence the average hydrate content of broad intervals containing more than one layer, not only because of the uncertainty in the layer-by-layer variation in lithology, but also because of the negative correlation in the errors of estimation of velocity between adjacent layers. In this investigation, an interval of about 20-m thickness (equivalent to between 2 and 5 layers in the model used for waveform inversion) was the smallest within which one could sensibly estimate the hydrate content. If lithological layering much thinner than 20-m thickness controls hydrate content, then hydrate concentrations within layers could significantly exceed or fall below the average values derived from seismic data.

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