Description: The migration of methane through the gas hydrate stability zone (GHSZ) in the marine subsurface is characterized by highly dynamic reactive transport processes coupled to thermodynamic phase transitions between solid gas hydrates, free methane gas, and dissolved methane in the aqueous phase. The marine subsurface is essentially a water-saturated porous medium where the thermodynamic instability of the hydrate phase can cause free gas pockets to appear and disappear locally, causing the model to degenerate. This poses serious convergence issues for the general-purpose nonlinear solvers (e.g., standard Newton), and often leads to extremely small time-step sizes. The convergence problem is particularly severe when the rate of hydrate phase change is much lower than the rate of gas dissolution. In order to overcome this numerical challenge, we have developed an all-at-once Newton scheme tailored to our gas hydrate model, which can handle rate-based hydrate phase change coupled with equilibrium gas dissolution in a mathematically consistent and robust manner.

Description: Cruise SO268 is fully integrated into the second phase of the European collaborative JPI-Oceans project MiningImpact and is designed to assess the environmental impacts of deep-sea mining of polymetallic nodules in the Clarion-Clipperton Fracture Zone (CCZ). In particular, the cruise aimed at conducting an independent scientific monitoring of the first industrial test of a pre-protoype nodule collector by the Belgian company DEME-GSR. The work includes collecting the required baseline data in the designated trial and reference sites in the Belgian and German contract areas, a quantification of the spatial and temporal spread of the produced sediment plume during the trials as well as a first assessment of the generated environmental impacts. However, during SO268 Leg 1 DEME-GSR informed us that the collector trials would not take place as scheduled due to unresolvable technical problems. Thus, we adjusted our work plan accordingly by implementing our backup plan. This involved conducting a small-scale sediment plume experiment with a small chain dredge to quantify the spatial and temporal dispersal of the suspended sediment particles, their concentration in the plume as well as the spatial footprint and thickness of the deposited sediment blanket on the seabed. Leg 1 and 2 acquired detailed environmental baseline data in the designated collector trial and reference sites as well as the site of the small-scale sediment plume experiment. The plume experiment was monitored by an array of acoustic and optical sensors and the impacted area was investigated in order to develop standards and protocols for impact assessments and recommendations for marine policy and international legislation. A more technical aim of the cruise was to test tools, technologies, and a concept for the environmental monitoring of future deep-sea mining operations. This comprised oceanographic, biological, microbiological, biogeochemical, and geologic investigations which required the deployment of a multitude of seagoing equipment, such as ROV Kiel 6000 for sampling of sediments, nodules, and benthic fauna as well as carrying out in situ measurements and experiments, and the deployment of the plume sensor array. AUV ABYSS and ROV Kiel 6000 were used for high-resolution acoustic mapping of the seafloor using mounted multibeam systems and video/photo surveys of the manganese nodule habitat. This work was accompanied by video observations with the OFOS system. Several benthic landers and moorings with acoustic and optical sensors were deployed and recovered for the measurements of physical and chemical oceanographic variables. Coring devices (i.e., box corer, gravity corer, TV-guided multiple corer, ROV-operaten push cores) were used to collect sediment samples for biological, geochemical, and microbiological analyses, and a CTD rosette water sampler, in situ pumps, and a bottom water sampler sampled the water column. In addition, recolonization experiments for nodule-associated fauna were started by deploying artificial hard substrates on the seabed of the working areas.

Description: The exchange of CH4 by CO2 in gas hydrates is of interest for the production of natural gas from methane hydrate with net zero climate gas balance, and for managing risks that are related to sediment destabilization and mobilization after gas-hydrate dissociation. Several experimental studies on the dynamics and efficiency of the process exist, but the results seem to be partly inconsistent. We used confocal Raman spectroscopy to map an area of several tens to hundreds µm of a CH4 hydrate sample during its exposure to liquid and gaseous CO2. On this scale, we could identify and follow different processes in the sample that occur in parallel. Next to guest-molecule exchange, gas-hydrate dissociation also contributes to the release of CH4. During our examination period, about 50% of the CO2 was bound by exchange for CH4 molecules, while the other half was bound by new formation of CO2 hydrates. We evaluated single gas-hydrate grains with confirmed gas exchange and applied a diffusion equation to quantify the process. Obtained diffusion coefficients are in the range of 10−13–10−18 m2/s. We propose to use this analytical diffusion equation for a simple and robust modeling of CH4 production by guest-molecule exchange and to combine it with an additional term for gas-hydrate dissociation.

Description: Seafloor heat flow measurements are utilized to determine the geothermal regime of the Danube deep-sea fan in the western Black Sea and are presented in the larger context of regional gas hydrate occurrences. Heat flow data were collected across paleo-channels in water depths of 550–1460 m. Heat flow across levees ranges from 25 to 30 mW m−2 but is up to 65 mW m−2 on channel floors. Gravity coring reveals sediment layers typical of the western Black Sea, consisting of three late Pleistocene to Holocene units, notably red clay within the lowermost unit cored. Heat flow derived from the bottom-simulating reflector (BSR), assumed to represent the base of the gas hydrate stability zone (GHSZ), deviates from seafloor measurements. These discrepancies are linked either to fast sedimentation or slumping and associated variations in sediment physical properties. Topographic effects account of up to 50% of heat flow deviations from average values. Combined with climate-induced variations in seafloor temperature and sea-level since the last glacial maximum large uncertainties in the prediction of the base of the GHSZ remain. A regional representative heat flow value is ~30 mW m−2 for the study region but deviations from this value may be up to 100%.

Description: A stratigraphic complex composed of mass transport deposits (MTDs), where the gas occurrence allows for the formation of a gas chimney and pipe structure, is identified based on seismic interpretation in the QiongDongNan area of the northern South China Sea. During the Fifth Gas Hydrate Drilling Expedition of the Guangzhou Marine Geological Survey, this type of complex morphology that has close interaction with local gas hydrate (GH) distribution was eventually confirmed. A flow-reaction model is built to explore the spatial–temporal matching evolution process of massive GH reservoirs since 30 kyr before the present (BP). Five time snapshots, including 30, 20, 10, and 5 kyr BP, as well as the present, have been selected to exhibit key strata-evolving information. The results of in situ tensile estimation imply fracturing emergence occurs mostly at 5 kyr BP. Six other environmental scenarios and three cases of paleo-hydrate existence have been compared. The results almost coincide with field GH distribution below the bottom MTD from drilling reports, and state layer fracturing behaviors always feed and probably propagate in shallow sediments. It can be concluded that this complex system with 10% pre-existing hydrates results in the exact distribution and occurrence in local fine-grained silty clay layers adjacent to upper MTDs.