Description: The recovery of natural gas from CH4-hydrate deposits in sub-marine and sub-permafrost environments through injection of CO2 is considered a suitable strategy towards emission-neutral energy production. This study shows that the injection of hot, supercritical CO2 is particularly promising. The addition of heat triggers the dissociation of CH4-hydrate while the CO2, once thermally equilibrated, reacts with the pore water and is retained in the reservoir as immobile CO2-hydrate. Furthermore, optimal reservoir conditions of pressure and temperature are constrained. Experiments were conducted in a high-pressure flow-through reactor at different sediment temperatures (2 °C, 8 °C, 10 °C) and hydrostatic pressures (8 MPa, 13 MPa). The efficiency of both, CH4 production and CO2 retention is best at 8 °C, 13 MPa. Here, both CO2- and CH4-hydrate as well as mixed hydrates can form. At 2 °C, the production process was less effective due to congestion of transport pathways through the sediment by rapidly forming CO2-hydrate. In contrast, at 10 °C CH4 production suffered from local increases in permeability and fast breakthrough of the injection fluid, thereby confining the accessibility to the CH4 pool to only the most prominent fluid channels. Mass and volume balancing of the collected gas and fluid stream identified gas mobilization as equally important process parameter in addition to the rates of methane hydrate dissociation and hydrate conversion. Thus, the combination of heat supply and CO2 injection in one supercritical phase helps to overcome the mass transfer limitations usually observed in experiments with cold liquid or gaseous CO2.

Description: The accumulation of methane hydrate in marine sediments is controlled by a number of physical and biogeochemical parameters including the thickness of the gas hydrate stability zone (GHSZ), the solubility of methane in pore fluids, the accumulation of particulate organic carbon at the seafloor, the kinetics of microbial organic matter degradation and methane generation in marine sediments, sediment compaction and the ascent of deep-seated 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 provided applying a transport-reaction model at global scale. The modeling and the data evaluation yield improved and better constrained estimates of the global pore volume within the modern GHSZ ( ≥ 44 × 1015 m3), the Holocene POC accumulation rate at the seabed (~1.4 × 1014 g yr−1), the global rate of microbial methane production in the deep biosphere (4−25 × 1012 g C yr−1) and the inventory of methane hydrates in marine sediments ( ≥ 455 Gt of methane-bound carbon).

Description: The thriving interest in harvesting deep-sea mineral resources, such as polymetallic nodules, calls for environmental impact studies and, ultimately, for regulations for environmental protection. Industrial-scale deep-sea mining of polymetallic nodules most likely has severe consequences for the natural environment. However, the effects of mining activities on deep-sea ecosystems, sediment geochemistry and element fluxes are still poorly understood. Predicting the environmental impact is challenging due to the scarcity of environmental baseline studies as well as the lack of mining trials with industrial mining equipment in the deep sea. Thus, currently we have to rely on small-scale disturbances simulating deep-sea mining activities as a first-order approximation to study the expected impacts on the abyssal environment. Here, we investigate surface sediments in disturbance tracks of seven small-scale benthic impact experiments, which have been performed in four European contract areas for the exploration of polymetallic nodules in the Clarion–Clipperton Zone (CCZ) in the NE Pacific. These small-scale disturbance experiments were performed 1 d to 37 years prior to our sampling program in the German, Polish, Belgian and French contract areas using different disturbance devices. We show that the depth distribution of solid-phase Mn in the upper 20 cm of the sediments in the CCZ provides a reliable tool for the determination of the disturbance depth, which has been proposed in a previous study from the SE Pacific (Paul et al., 2018). We found that the upper 5–15 cm of the sediments was removed during various small-scale disturbance experiments in the different exploration contract areas. Transient transport-reaction modeling for the Polish and German contract areas reveals that the removal of the surface sediments is associated with the loss of the reactive labile total organic carbon (TOC) fraction. As a result, oxygen consumption rates decrease significantly after the removal of the surface sediments, and, consequently, oxygen penetrates up to 10-fold deeper into the sediments, inhibiting denitrification and Mn(IV) reduction. Our model results show that the return to steady-state geochemical conditions after the disturbance is controlled by diffusion until the reactive labile TOC fraction in the surface sediments is partly re-established and the biogeochemical processes commence. While the reestablishment of bioturbation is essential, steady-state geochemical conditions are ultimately controlled by the delivery rate of organic matter to the seafloor. Hence, under current depositional conditions, new steady-state geochemical conditions in the sediments of the CCZ are reached only on a millennium scale even for these small-scale disturbances simulating deep-sea mining activities.