Description: Highlights • The SUGAR project has developed and tested various methods for gas production from marine gas hydrates from micro to field scale. • Numerical simulations improved the understanding of processes on molecular to reservoir scale. • Depressurization is a promising technology for exploiting gas hydrate deposits in the Danube Delta. • The injection of CO2 or CO2–N2 is not a suitable method for the exploitation of gas hydrate deposits in the Danube Delta. Abstract One important scientific objective of the national research project SUGAR – Submarine Gas Hydrate Reservoirs was the development, improvement, and test of innovative concepts for the production of methane from natural gas hydrate reservoirs. Therefore, different production methods, such as the thermal stimulation using in situ combustion, the chemical stimulation via injection of CO2 as a gaseous, liquid or supercritical phase and depressurization were tested alone or in combination at different scales. In the laboratory experiments these ranged from pore and hydrate grain scale to 425-L reactor volume, whereas numerical models were applied to describe the related processes from molecular to reservoir scale. In addition, the numerical simulations also evaluated the feasibility and efficiency of the application of these methods in selected areas, such as the Danube Paleodelta in the Black Sea, addressing the two dominant methane hydrate reservoir settings, buried channel-levee and turbidite systems. It turned out, that the injection of CO2 or a CO2–N2 gas mixture is not applicable for the Danube Paleodelta in the Black Sea, because the local pressure and temperature conditions are too close to the equilibrium conditions of both, the CO2 hydrate and a CO2–N2 mixed hydrate stability fields. Experiments using thermal stimulation and depressurization showed promising results but also some issues, such as sufficient heat transfer. In summary it can be said that the applicability and efficiency of each method has to be proven for each specific hydrate reservoir conditions. Based on the results obtained by numerical simulations the most promising and safe method for the production of CH4 from hydrate bearing sediments in the Danube Paleodelta would be the depressurization technique. This study summarizes the main experimental and modeling results.

Description: Highlights • The effects of the combined method on HBS geomechanical properties were examined. • Mechanical behavior depended on dissociation ratios and GH saturations. • Mechanical strength of the replaced HBSs was significantly recovered. • The combination of depressurization and replacement increased total CH4 recovery. • Optimum replacement occurred at a dissociation ratio of 20% with CO2 injection. Abstract This study analyzed the potential effects of gas hydrate (GH) exploitation on the geomechanical properties of hydrate-bearing sediment (HBS) by examining the combined effects of depressurization and CO2 injection using triaxial compression tests. The stress-strain behavior of the initial CH4 HBS showed strong hardening-softening characteristics and high peak strength, whereas milder hardening-softening behavior and reduced peak strength were observed after partial (20, 40, 60, and 80%) or complete GH dissociation (100%), indicating that the mechanical behavior clearly depended on dissociation ratios and GH saturations. In response to CO2 injection in partially dissociated HBS, subsequent CH4–CO2 hydrate exchange, and secondary CO2 hydrate formation, the mechanical strength of the replaced HBS recovered significantly, and stress-strain characteristics were similar to that of the 20% dissociated CH4 HBS. Although total CH4 recovery was increased by the combination of depressurization and replacement, optimum recovery was found at a dissociation ratio of 20% followed by replacement because production by replacement decreased as the dissociation ratio increased. These results contribute to the understanding of how depressurization and CO2 injection schemes may be combined to optimize energy recovery and CO2 sequestration. In particular, this research demonstrates that CH4–CO2 hydrate exchange and secondary GH formation are suitable methods for controlling and maintaining the mechanical stability of HBSs.

Description: Highlights • MeBo drilling in Danube fan down to 147 m recovered limnic to marine deposits. • Molecular and stable isotope characterization of light hydrocarbons, CO2, and H2O. • H and O isotopic compositions of pore water reflect paleoclimate variations. • Isotope relations prove microbial carbonate reduction as major methanogenic pathway. • Control of δ2H–CH4 by δ2H–H2O may lead to misinterpretation of methanogenic paths. Abstract We report on the geochemistry of light hydrocarbons and pore water in sediments down to 147 m below seafloor (mbsf), at two sites within the gas hydrate stability field of the Danube deep-sea fan, Black Sea. Sediments were drilled with MARUM-MeBo200 and comprise the transition from limnic to the recent marine stage. Stable C/N ratios (mean 5.1 and 5.6) and δ13C-Corg values (mean −25.8‰ V-PDB) suggest relatively uniform bulk organic matter compositions. In contrast, pore water δ2H and δ18O values varied considerably from approx. −120‰ to −30‰ V-SMOW and from −15‰ to −3‰ V-SMOW, respectively. These data pairs plot close to the ‘Global Meteoric Water Line’ and indicate paleo temperature variations. Depletions of pore water in 2H and 18O below 40 mbsf indicate low temperatures and likely reflect conditions during (the) last glacial period(s). Methane was much more abundant than the only other hydrocarbons found in notable concentrations, ethane and propane ((C1/(C2+C3) ≥20,000). Relatively constant δ13C–CH4 (~−70‰ V-PDB) and δ13C–C2H6 (~−52‰ V-PDB) values with depth indicate that methane and ethane are predominantly of microbial origin and that their formation was not limited by carbon availability. In contrast, δ2H–CH4 values varied in a large range (approx. −310 to −240‰ V-SMOW) with depth and positively correlated with trends observed for δ2H–H2O. Isotope separations (Δδ13C(CH4–CO2), Δδ2H(CH4–H2O)) substantiate that microbial carbonate reduction (CR) is the prevalent methanogenic pathway throughout the sediments irrespective of their geochemical history. Remarkably, in δ13C–CH4 – δ2H–CH4 diagrams widely used, samples characterized by δ2H–CH4 values more negative than approx. −250‰ plot out of the field assigned for pure CR. We conclude that assignments of microbial methanogenic pathways based on classical interpretations of δ13C–CH4 – δ2H–CH4 pairs can lead to misinterpretations, as severe 2H-depletions of methane formed through microbial CR can result from 2H-depletions of the pore water generated during low-temperature climatic periods.

Description: Highlights • Approaches for CO2 leakage detection, attribution and quantification monitoring exist. • Many approaches cover multiple monitoring tasks simultaneously. • Sonars and chemical sensors on ships or AUVs can cover large areas. • Newer, more specific technologies can detect, verify and quantify smaller, localised leaks. Environmental monitoring of offshore Carbon Capture and Storage (CCS) complexes requires robust methodologies and cost-effective tools to detect, attribute and quantify CO2 leakage in the unlikely event it occurs from a sub-seafloor reservoir. Various approaches can be utilised for environmental CCS monitoring, but their capabilities are often undemonstrated and more detailed monitoring strategies need to be developed. We tested and compared different approaches in an offshore setting using a CO2 release experiment conducted at 120 m water depth in the Central North Sea. Tests were carried out over a range of CO2 injection rates (6 - 143 kg d−1) comparable to emission rates observed from abandoned wells. Here, we discuss the benefits and challenges of the tested approaches and compare their relative cost, temporal and spatial resolution, technology readiness level and sensitivity to leakage. The individual approaches demonstrate a high level of sensitivity and certainty and cover a wide range of operational requirements. Additionally, we refer to a set of generic requirements for site-specific baseline surveys that will aid in the interpretation of the results. Critically, we show that the capability of most techniques to detect and quantify leakage exceeds the currently existing legal requirements.

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: Deep-sea mining may be just a few years away and yet society is struggling to assess the positive aspects, such as increasing the supply of metals for battery production to fuel the green revolution, versus the potentially large environmental impacts. Mining of polymetallic (manganese) nodules from the deep ocean is likely to be the first mineral resource targeted and will involve direct impacts to hundreds of km2 of seabed per mine per year. However, the mining activity will also cause the generation of large sediment plumes that will spread away from the mine site and have both immediate and long-term effects over much wider areas. We discuss what the impacts of plumes generated near the seabed by mining vehicles may be and how they might be measured in such challenging environments. Several different mining vehicles are under development around the world and depending on their design some may create larger plumes than others. We discuss how these vehicles could be compared so that better engineering designs could be selected and to encourage innovation in dealing with plume generation and spread. These considerations will aid the International Seabed Authority (ISA) that has the task of regulating mining activities in much of the deep sea in its commitment to promote the Best Available Technology (BAT) and Best Environmental Practice (BEP).

Description: A comprehensive understanding of the deep-sea environment and mining’s likely impacts is necessary to assess whether and under what conditions deep-seabed mining operations comply with the International Seabed Authority’s obligations to prevent ‘serious harm’ and ensure the ‘effective protection of the marine environment from harmful effects’ in accordance with the United Nations Convention on the Law of the Sea. A synthesis of the peer-reviewed literature and consultations with deep-seabed mining stakeholders revealed that, despite an increase in deep-sea research, there are few categories of publicly available scientific knowledge comprehensive enough to enable evidence-based decision-making regarding environmental management, including whether to proceed with mining in regions where exploration contracts have been granted by the International Seabed Authority. Further information on deep-sea environmental baselines and mining impacts is critical for this emerging industry. Closing the scientific gaps related to deep-seabed mining is a monumental task that is essential to fulfilling the overarching obligation to prevent serious harm and ensure effective protection, and will require clear direction, substantial resources, and robust coordination and collaboration. Based on the information gathered, we propose a potential high-level road map of activities that could stimulate a much-needed discussion on the steps that should be taken to close key scientific gaps before any exploitation is considered. These steps include the definition of environmental goals and objectives, the establishment of an international research agenda to generate new deep-sea environmental, biological, and ecological information, and the synthesis of data that already exist.

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: Highlights • Surface sediments react quickly with leaking CO2 and release cations into porewaters. • Both carbonate and silicate mineral dissolution lead to neutralization of CO2 in the sediments. • During short-term exposure to CO2 no toxic substances were released from North Sea surface sediments. • Porewater composition can be used as a diagnostic indicator of CO2 leakage from storage reservoirs. Abstract Sub-seabed geological CO2 storage is discussed as a climate mitigation strategy, but the impact of any leakage of stored CO2 into the marine environment is not well known. In this study, leakage from a CO2 storage reservoir through near-surface sediments was mimicked for low leakage rates in the North Sea. Field data were combined with laboratory experiments and transport-reaction modelling to estimate CO2 and mineral dissolution rates, and to assess the mobilization of metals in contact with CO2-rich fluids and their potential impact on the environment. We found that carbonate and silicate minerals reacted quickly with the dissolved CO2, increasing porewater alkalinity and neutralizing about 5% of the injected CO2. The release of Ca, Sr, Ba and Mn was mainly controlled by carbonate dissolution, while Fe, Li, B, Mg, and Si were released from silicate minerals, mainly from deeper sediment layers. No toxic metals were released from the sediments and overall the injected CO2 was only detected up to 1 m away from seabed CO2 bubble streams. Our results suggest that low leakage rates of CO2 over short timescales have minimal impact on the benthic environment. However, porewater composition and temperature are effective indicators for leakage detection, even at low CO2 leakage rates.

Description: Predictability of the dispersion of sediment plumes induced by potential deep-sea mining activities is still very limited due to operational limitations on in-situ observations required for a thorough validation and calibration of numerical models. Here we report on a plume dispersion experiment carried out in the German license area for the exploration of polymetallic nodules in the northeastern tropical Pacific Ocean in 4,200 m water depth. The dispersion of a sediment plume induced by a small-scale dredge experiment in April 2019 was investigated numerically by employing a sediment transport module coupled to a high-resolution hydrodynamic regional ocean model. Various aspects including sediment characteristics and ocean hydrodynamics were examined to obtain the best statistical agreement between sensor-based observations and model results. Results show that the model is capable of reproducing suspended sediment concentration and redeposition patterns observed during the dredge experiment. Due to a strong southward current during the dredging, the model predicts no sediment deposition and plume dispersion north of the dredging tracks. The sediment redeposition thickness reaches up to 9 mm directly next to the dredging tracks and 0.07 mm in about 320 m away from the dredging center. The model results suggest that seabed topography and variable sediment release heights above the seafloor cause significant changes especially for the low sedimentation pattern in the far-field area. Near-bottom mixing is expected to strongly influence vertical transport of suspended sediment.