Description: The knowledge of the phase behavior of carbon dioxide (CO2)-rich mixtures is a key factor to understand the chemistry and migration of natural volcanic CO2 seeps in the marine environment, as well as to develop engineering processes for CO2 sequestration coupled to methane (CH4) production from gas hydrate deposits. In both cases, it is important to gain insights into the interactions of the CO2-rich phase—liquid or gas—with the aqueous medium (H2O) in the pore space below the seafloor or in the ocean. Thus, the CH4-CO2 binary and CH4-CO2-H2O ternary mixtures were investigated at relevant pressure and temperature conditions. The solubility of CH4 in liquid CO2 (vapor-liquid equilibrium) was determined in laboratory experiments and then modelled with the Soave–Redlich–Kwong equation of state (EoS) consisting of an optimized binary interaction parameter kij(CH4-CO2) = 1.32 × 10−3 × T − 0.251 describing the non-ideality of the mixture. The hydrate-liquid-liquid equilibrium (HLLE) was measured in addition to the composition of the CO2-rich fluid phase in the presence of H2O. In contrast to the behavior in the presence of vapor, gas hydrates become more stable when increasing the CH4 content, and the relative proportion of CH4 to CO2 decreases in the CO2-rich phase after gas hydrate formation.

Description: This article presents gas hydrate experimental measurements for mixtures containing methane (CH4), carbon dioxide (CO2) and nitrogen (N2) with the aim to better understand the impact of water (H2O) on the phase equilibrium. Some of these phase equilibrium experiments were carried out with a very high water-to-gas ratio that shifts the gas hydrate dissociation points to higher pressures. This is due to the significantly different solubilities of the different guest molecules in liquid H2O. A second experiment focused on CH4-CO2 exchange between the hydrate and the vapor phases at moderate pressures. The results show a high retention of CO2 in the gas hydrate phase with small pressure variations within the first hours. However, for our system containing 10.2 g of H2O full conversion of the CH4 hydrate grains to CO2 hydrate is estimated to require 40 days. This delay is attributed to the shrinking core effect, where initially an outer layer of CO2-rich hydrate is formed that effectively slows down the further gas exchange between the vapor phase and the inner core of the CH4-rich hydrate grain.

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: Deep-sea mining for polymetallic nodules is expected to have severe environmental impacts because not only nodules but also benthic fauna and the upper reactive sediment layer are removed through the mining operation and blanketed by resettling material from the suspended sediment plume. This study aims to provide a holistic assessment of the biogeochemical recovery after a disturbance event by applying prognostic simulations based on an updated diagenetic background model and validated against novel data on microbiological processes. It was found that the recovery strongly depends on the impact type; complete removal of the reactive surface sediment reduces benthic release of nutrients over centuries, while geochemical processes after resuspension and mixing of the surface sediment are near the pre-impact state 1 year after the disturbance. Furthermore, the geochemical impact in the DISturbance and reCOLonization (DISCOL) experiment area would be mitigated to some degree by a clay-bound Fe(II)-reaction layer, impeding the downward diffusion of oxygen, thus stabilizing the redox zonation of the sediment during transient post-impact recovery. The interdisciplinary (geochemical, numerical and biological) approach highlights the closely linked nature of benthic ecosystem functions, e.g. through bioturbation, microbial biomass and nutrient fluxes, which is also of great importance for the system recovery. It is, however, important to note that the nodule ecosystem may never recover to the pre-impact state without the essential hard substrate and will instead be dominated by different faunal communities, functions and services.

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 conceived. 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). These small-scale disturbance experiments were performed 1 day 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 (Paul et al., 2018). We found that the upper 5–15 cm of the sediments were removed during various small-scale disturbance experiments in the different exploration contract areas. Transient transport-reaction modelling for the Polish and German contract areas reveals that the removal of the surface sediments is associated with the loss of reactive labile organic carbon. As a result, oxygen consumption rates decrease significantly after the removal of the surface sediments, and consequently, oxygen penetrates up to tenfold deeper into the sediments inhibiting denitrification and Mn(IV) reduction. Our model results show that the post-disturbance geochemical re-equilibration 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 re-establishment of bioturbation is essential, the geochemical re-equilibration of the sediments is ultimately controlled by the burial rates of organic matter. Hence, under current depositional conditions, the new geochemical equilibrium in the sediments of the CCZ is reached only on a millennia scale even for these small-scale disturbances simulating deep-sea mining activities.

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: 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%.