Beschreibung: 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.

Beschreibung: Deep-seabed polymetallic nodule mining can have multiple adverse effects on benthic communities, such as permanent loss of habitat by removal of nodules and habitat modification of sediments. One tool to manage biodiversity risks is the mitigation hierarchy, including avoidance, minimization of impacts, rehabilitation and/or restoration, and offset. We initiated long-term restoration experiments at sites in polymetallic nodule exploration contract areas in the Clarion-Clipperton Zone that were (i) cleared of nodules by a preprototype mining vehicle, (ii) disturbed by dredge or sledge, (iii) undisturbed, and (iv) naturally devoid of nodules. To accommodate for habitat loss, we deployed 〉2000 artificial ceramic nodules to study the possible effect of substrate provision on the recovery of biota and its impact on sediment biogeochemistry. Seventy-five nodules were recovered after eight weeks and had not been colonized by any sessile epifauna. All other nodules will remain on the seafloor for several years before recovery. Furthermore, to account for habitat modification of the top sediment layer, sediment in an epibenthic sledge track was loosened by a metal rake to test the feasibility of sediment decompaction to facilitate soft-sediment recovery. Analyses of granulometry and nutrients one month after sediment decompaction revealed that sand fractions are proportionally lower within the decompacted samples, whereas total organic carbon values are higher. Considering the slow natural recovery rates of deep-sea communities, these experiments represent the beginning of a ~30-year study during which we expect to gain insights into the nature and timing of the development of hard-substrate communities and the influence of nodules on the recovery of disturbed sediment communities. Results will help us understand adverse long-term effects of nodule removal, providing an evidence base for setting criteria for the definition of “serious harm” to the environment. Furthermore, accompanying research is needed to define a robust ecosystem baseline in order to effectively identify restoration success.

Beschreibung: 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.

Beschreibung: 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%.