Description: The simultaneous and independent determination of the radiogenic (87Sr/86Sr) and the fractionation reflecting stable (!88/86Sr) Sr isotope ratio on pore waters, sediments and precipitates (e.g. carbonates and sulfates) opens a new perspective in the field of submarine weathering and Sr contribution to the ocean chemistry. Four initial case studies covering (1.) CO2 seeps of the Okinawa Trough (OT), (2.) mud volcanoes (MV) and mounds in the Gulf of Cadiz (GoC) and the (3.) Central American Fore Arc as well as first results from the (4.) Black Sea are conducted and reflect a stable Sr perspective on seeps from a broad range of geological settings. Referred to NIST-SRM-987, in this study the IAPSO seawater (SW) standard has a !88/86Sr of 0.39 ‰ (±0.03, 2SD). As a prominent systematic deviation the OT pore water (PW) data from a site with CO2 hydrate and liquid CO2 occurence show values ranging from 0.27 to 0.59 ‰ (286 to 64 cm sediment depth), accompanied by a weak inversely correlated trend from 0.2 to 0.15 ‰ for the corresponding bulk sediment (286 to 36 cm). In contradiction to a simple fluid/SW-mixing approach as driving mechanism for the PW stable Sr trend the 87Sr/86Sr signature stays within analytical uncertainty constant with depth (0.70980 (1)) and differs significantly from SW (0.70917 (1)) and the more radiogenic, slightly heterogeneous sediment (0.71892-0.71731). Potential explanation for the observed !88/86Sr trend and PW signatures heavier than SW are (a) strong fractionation processes enriching light isotopes in secondary precipitates and remineralisation products and heavier signatures in the remaining fluid and/or (b) preferential dissolution of heavier mineral phases. Examples for the latter kind of sediment component are determined in a detailed study of the Mercator MV (GoC) by high !88/86Sr ratios of 0.72 for authigenic and 0.92 ‰ for potentially extruded gypsum crystals. Combined with PW data from the other seep settings (0.2 to 0.52 ‰) a broad range of Sr contribution and fractionation processes becomes evident.

Description: Commercial utilization of methane hydrate deposits in the seabed: The vast amount of natural gas bound in methane hydrates is considered as future energy resource by a growing number of states and companies in South-East Asia and North America. Successful field production tests showed that gas hydrates can be dissociated in the sub-surface by heat addition and pressure reduction while the released gas is produced via conventional drill wells. Laboratory studies demonstrate that CO2 from coal power plants can be applied to liberate methane from the hydrate structure and produce natural gas while the injected CO2 is safely stored as hydrate in the sub-surface. The commercial exploitation of sub-seabed gas hydrates may start in the next decade pending on the success of field production tests off Japan scheduled for 2012 and 2014. Specific environmental risks are associated with the future utilization of gas hydrates. These include the extinction of special benthic ecosystems relying on methane from hydrates as energy source, the triggering of slope failure, and leakage of greenhouse gases into the marine environment. Suitable measures have to be taken to avoid these risks. An appropriate legal framework should be established at the international level to meet the specific challenges and risks associated with the commercial use of gas hydrates in the marine environment.

Description: Within the German gas hydrate initiative SUGAR, we have developed a new tool for predicting the formation of sub-seafloor gas hydrate deposits. For this purpose, a new 2D/3D module simulating the biogenic generation of methane from organic material and the formation of gas hydrates has been added to the petroleum systems modeling software package PetroMod®. T ypically, PetroMod® simulates the thermogenic generation of multiple hydrocarbon components including oil and gas, their migration through geological strata, and finally predicts the oil and gas accumulation in suitable reservoir formations. We have extended PetroMod® to simulate gas hydrate accumulations in marine and permafrost environments by the implementation of algorithms describing (1) the physical, thermodynamic, and kinetic properties of gas hydrates; and (2) a kinetic continuum model for the microbially mediated, low temperature degradation of particulate organic carbon in sediments. Additionally, the temporal and spatial resolutions of PetroMod® were increased in order to simulate processes on time scales of hundreds of years and within decimeters of spatial extension. As a first test case for validating and improving the abilities of the new hydrate module, the petroleum systems model of the Alaska North Slope developed by IES (currently Shlumberger) and the USGS has been chosen. In this area, gas hydrates have been drilled in several wells, and a field test for hydrate production is planned for 2011/2012. The results of the simulation runs in PetroMod® predicting the thickness of the gas hydrate stability field, the generation and migration of biogenic and thermogenic methane gas, and its accumulation as gas hydrates will be shown during the conference. The predicted distribution of gas hydrates will be discussed in comparison to recent gas hydrate findings in the Alaska North Slope region.

Description: The accumulation of methane hydrate in marine sediments is basically controlled by the accumulation of particulate organic carbon at the seafloor, the kinetics of microbial organic matter degradation and methane generation in marine sediments, the thickness of the gas hydrate stability zone (GHSZ), the solubility of methane in pore fluids within the GHSZ and the ascent of deepseated pore fluids and methane gas into the GHSZ. Our present knowledge on these controlling factors is discussed and new estimates of global sediment and methane fluxes are presented. A new transport-reaction model is applied at a global grid defined by these up- dated parameter values. The model yields an improved and better constrained estimate of the global inventory of methane gas hydrates in marine sediments (3000 ± 2000 Gt of methane carbon).

Description: The production of natural gas via injection of fossil-fuel derived CO2 into submarine gas hydrate reservoirs can be an example of tapping a hydrocarbon energy source in a CO2-neutral manner. However, the industrial application of this method is technically challenging. Thus, prior to feasibility testing in the field, multi-scale laboratory experiments and adapted reaction-modeling are needed. To this end, high-pressure flow-through reactors of 15 and 2000 mL sample volume were constructed and tested. Process parameters (P, T, Q, fluid composition) are defined by a fluid supply and conditioning unit to enable simulation of natural fluid-flow scenarios for a broad range of sedimentary settings. Additional Raman- and NMR-spectroscopy aid in identifying the most efficient pathway for CH4 extraction from hydrates via CO2 injection on both microscopic and macroscopic level. In this study we present experimental set-up and design of the highpressure flow-through reactors as well as CH4 yields from H4-hydrate decomposition experiments using CO2-rich brines and pure liquefied CO2.

Description: Mud volcanoes are seafloor expressions of focused fluid flow that are common in compressional tectonic settings. New high-resolution 3-D seismic data from the Mercator mud volcano (MMV) and an adjacent buried mud volcano (BMV) image the internal structure of the top 800 m of sediment at both mud volcanoes, revealing that both are linked and have been active episodically. The total volumes of extruded mud range between 0.15 and 0.35 km3 and 0.02–0.05 km3 for the MMV and the BMV, respectively. The pore water composition of surface sediment samples suggests that halokinesis has played an important role in the evolution of the mud volcanoes. We propose that erosion of the top of the Vernadsky Ridge that underlies the mud volcanoes activated salt movement, triggering deep migration of fluids, dissolution of salt, and sediment liquefaction and mobilization since the end of the Pliocene. Since beginning of mud volcanism in this area, the mud volcanoes erupted four times while there was only one reactivation of salt tectonics. This implies that there are other mechanisms that trigger mud eruptions. The stratigraphic relationship of mudflows from the MMV and BMV indicates that the BMV was triggered by the MMV eruptions. This may either be caused by loading-induced hydrofracturing within the BMV or due to a common feeder system for both mud volcanoes. This study shows that the mud volcanoes in the El Arraiche mud volcano field are long-lived features that erupt with intervals of several tens of thousands of years.