Understanding the deep biosphere is of great commercial and scientific interest and will contri-bute to increased knowledge of the environment. If environmentally relevant results are to be ob-tained the precondition to achieve genuine findings is research in pristine habitat as close as pos-sible to those encountered in-situ. Therefore benthic conditions of sediment structure and gas hydrates, temperature, pressure and bio-geochemistry have to be maintained during the sequences of sampling, retrieval, transfer, sto-rage and downstream analysis. At the Technische Universität Berlin (TUB) the Pressurized Core Sub-Sampling and Extrusion System (PRESS) was developed in the EU project HYACE/HYACINTH. It enables well-defined sectioning and transfer of drilled pressure-cores [obtained by HYACE Rotary Corer (HRC) and Fugro Pressure Corer (FPC)] into transportation and investigation chambers. Coupled with DeepIsoBUG (University Cardiff, John Parkes) it allows sub-sampling and incubation of coaxial core-sections to examine high-pressure adapted bacteria or remote biogeochemical processes in defined research conditions of the laboratory; all sterile, anaerobic and without depressurisation. Appraisals of successful PRESS deployments in the Gulf of Mexico, on IODP Expedition 311 and as part of the NGHP expedition 01 demonstrate the general concept to be feasible and useful. Aided by Deutsche Forschungsgemeinschaft (DFG) TUB is currently working on concepts to downscale the system in order to reduce logistical and financial expenses and, likewise, to enlarge its implementation by requiring less operating space. Redesigning the cutting mechanism shall simultaneously adjust the system to harder cores (e.g., ICDP). Novel transportation chambers for processed sub-samples intend to make the system more attractive for a broad spectrum of users and reduce their interdependence.

In this work the nucleation kinetics of propane gas hydrate has been investigated experimentally using a stirred batch reactor. The experiments have been performed isothermally recording the pressure as a function of time. Experiments were conducted at different stirring rates, but in the same supersaturation region. The experiments showed that the gas dissolution rate rather than the induction time of propane hydrate is influenced by a change in the stirring rate. This was especially valid at high stirring rates when the water surface was severely disturbed. Addition of polyvinylpyrrolidone to the aqueous phase was found to reduce the gas dissolution rate slightly, however the induction times were prolonged quite substantially. The induction time data were correlated using a newly developed induction time model based on crystallization theory also capable of taking into account the presence of additives. In most cases reasonable agreement between the data and the model could be obtained. The results revealed that especially the effective surface energy between propane hydrate and water is likely to change when the stirring rate varies from very high to low. The prolongation of induction times according to the model is likely to be due to a change in the nuclei-substrate contact angle.

Occurrences of carbonate-cemented nodules and concretions exposed on the seafloor that contain cements with light carbon isotopes, indicating a contribution of methane-derived carbon, are commonly interpreted to be indicators of seafloor fluid venting. Thus, their presence is commonly used as an indicator of the possible occurrence of methane gas hydrate within the near subsurface. While some of these carbonates exhibit facies that require formation on the seafloor, the dominant fine-grained lithology associated with these carbonates indicates they were formed as sedimenthosted nodules within the subsurface and are similar to nodules that are obtained from the subsurface in Deep Sea Drilling Project, Ocean Drilling Project, and Integrated Ocean Drilling Project boreholes. Here we present the hypothesis that the occurrence of these carbonates on the seafloor may instead indicate areas of persistent seafloor erosion.

The chemical structure of polyether amines (PEA), mainly electron donating multiple oxygen and nitrogen atoms as well as active hydrogen atoms, make such compounds actively participating in the formation of hydrogen bonds with surrounding molecules. Hydrophobic polypropylene glycol functionality gives PEA's properties of multi-headed surfactants having hydrophilic amine groups. These groups have a strong affinity for water molecules, ice and hydrate crystals. Such PEA compounds have been known for several years. However, the hydrate inhibition properties of PEA’s were only discovered about twelve years ago. The first discovery stimulated more research in laboratories and led to practical applications for hydrate inhibition in gas fields. An interesting property of PEAs is their synergistic effect on hydrate inhibition when applied concurrently with polymeric kinetic hydrate inhibitors (KHI) or thermodynamic inhibitors (THI). The combination inhibitors are better inhibitors than a single component one. Quaternized polyether diamines are efficient antiagglomerant (AA) hydrate inhibitors while different derivatization can produce dual functionality compounds, i.e. corrosion inhibitors/gas hydrate inhibitors (CI/GHI). With all of this versatility, PEAs found application for hydrate inhibition in oil and gas fields onshore and offshore in production, flowlines and completion. The PEAs have an excellent record in protecting gas-producing wells from plugging with hydrates. (Final corrected copy of ICGH paper 5347)

On the lower continental slope off Vancouver Island near scientific ocean drilling IODP Site U1326, traveltime modeling along several ocean bottom seismograph (OBS) profiles shows anomalous high velocities of about 2.0 km/s at 70 - 100 m depth (compared to a no-hydrate reference of about 1.6 km/s). These velocities are consistent with the Site U1326 downhole sonic logs that show velocities up to 2.8 km/s near these depths. The drillhole high velocities are interpreted as caused by nearly massive hydrate with concentrations as large as 60-80% of the pore space. The OBS seismic velocities show that high hydrate concentrations of at least 20-30% are laterally extensive out to distances of at least 6 km on either side of the drillhole. A grid of migrated single-channel data shows a sequence of 15- to 75-m-high seafloor scarps, cutting across the ridge perpendicular to the deformation front. These are interpreted as normal faults. Two of the largest fault scarps bound a prominent ~2.5-km-wide slump feature on the steep seaward slope of the frontal ridge. This provides strong evidence that the slump is fault-controlled, and the base of the slump is near the base of hydrate stability suggesting that the slumping is also related to the presence of gas hydrate. At IODP drill Site U1327 on the mid-continental slope, seismic data were recorded along a 1-km-long profile of 10 OBSs. Traveltimes from wide-angle and vertical-incidence arrivals were inverted simultaneously for velocity structure. Corresponding hydrate concentrations increase with depth with an average of about 15% in the 100-m-thick layer above the base of hydrate stability . The seismic structure shows that this local hydrate distribution extends on the kilometer-scale away from the drillhole, as also suggested by multichannel interval velocities in the region. At Site U1328 (Bullseye Vent), seismic images derived from the very high resolution deep-towed DTAGS reflection data show that the top of a zone of high reflectivity, 10-25 m in thickness, extends from the seafloor to a depth of ~30 m. This zone likely corresponds to the shallow region of massive methane hydrate detected in the upper 40 m in the drillhole, and may represent a system of fractures through which fluids and gas pass from the main vent to the seafloor.

For a number of years the NRC group has been working on a laboratory protocol for the analysis of gas hydrate that has been recovered from various natural sites. The expectation was that a comprehensive set of techniques would become available for the general use of hydrate researchers around the world. With the current set of available techniques a good picture of natural gas hydrates can be obtained, although the emerging complexity of the hydrate-mineral system still demands additional work. Here we present a suite of techniques that will take a researcher from preservation techniques to hydrate occurrence, gas/water/sediment ratios, gas and isotope analysis, P-T behaviour, structure, composition, degree of water conversion to hydrate, hydrate homogeneity and decomposition behaviour. As more detailed studies become possible a variety of more subtle features are revealed, for instance the role of minor gas components in hydrate stability, decomposition behaviour and heterogeneity in structure and composition.

Solid State NMR spectroscopy has taken a very prominent place among the many spectroscopic techniques employed for the characterization of clathrate hydrates. Exceptionally high sensitivity of the spectra to the molecular environment and dynamic processes, together with the ability to provide accurate and quantitative data make NMR spectroscopy a highly desirable and versatile approach for studying hydrates. Application of the method to its full capacity, however, requires some extensive instrumental developments to adapt it to the specific experimental requirements of hydrate studies, for example, very low temperatures and high pressures. In this presentation we will give an overview of recent Solid State NMR advances in various areas of hydrate research. Examples will include analysis of the composition and structure of mixed gas hydrates prepared from multi-component mixtures of hydrocarbons, characterization of the natural gas hydrates from different sources, and evaluation of formation conditions and properties of mixed hydrogen hydrates. 13C NMR with Magic Angle Spinning (MAS) at -100C has been the main approach in the first two examples. We will discuss the requirements and the necessary instrumental developments to make the experiments of this type successful. The detailed characterization of mixed hydrogen hydrates required low temperature 1H MAS. Problems of quantification in these experiments will be discussed. We expect that all these recent experimental developments will prompt wider application of Solid State NMR in hydrate research.

Electronic structure calculations are performed to determine the barriers to migration of molecular hydrogen in clathrate cages. The barriers are used in a chemical reaction rate expression to determine the rate of H2 migration and the diffusion coefficient for the hydrogen guest molecules. Calculations are performed for migration of hydrogen guests through pentagonal and hexagonal clathrate cage faces. Cage faces where the water molecules obey the water rules and cage faces with Bjerrum L and D defects are considered. The migration barriers were calculated to be ≈25 kcal/mol from the pentagonal faces and between 5 to 6 kcal/mol for the hexagonal faces, depending on the orientation of the hydrogen molecule.

A series of studies have been carried out to elucidate the sediment effect on the saturation level of methane hydrate in sediments. The specimens tested covered most of the natural sediment types, with various combinations of particle size and mineral composition. The results obtained indicate that particle size and clay contents are the two key factors determining the saturation level of gas hydrate in sediments: the finer the particle size and/or the higher the clay content, the lower the hydrate saturation. The observed particle size effect and clay effect on hydrate saturation can be accredited to the specific surface area of a sediment.

This contribution aims to publicize the efforts made in the identification of gas hydrates in the Uruguayan continental shelf, analyze the most outstanding aspects related to its energy potential, as well as include this topic in other areas of knowledge for a comprehensive understanding of the subject. The hydrates, crystalline solid formed mainly by water and natural gas, are reservoirs of carbon that occur naturally in the continents in permafrost areas, and at sea, in the offshore basins of continental margins. They contain more than twice the total carbon in the world, surpassing the conventional hydrocarbon reserves. Principal energy programs foresee its commercial exploitation by 2015. International research programs include not only the energy aspect, but studying such systems considering their participation in the global carbon cycle, climate change and benthic communities associated with them. In our country, several seismic surveys showed evidence of the presence of gas hydrates in continental shelf and the surrounding area. The first survey was carried out by Brazil in the south of the Brazilian continental shelf, ANCAP then showed the continuity of the hydrate layer on the Uruguayan continental shelf and estimated the gas potential of the mineralized layer (87 TCF). Finally, the BGR survey verified the existence of seismic evidence of gas hydrates layer and the presence of free gas below these. The typical seismic response of gas hydrate and free gas is the BSR (Bottom Simulating Reflector) and is interpreted as a positive intensity reflection, followed by a negative intensity, showing the wave passage from a high acoustic impedance zone to a low acoustic impedance zone.