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: 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: The presence of gas hydrates is well known in the marine realm southwest off Taiwan due to the widespread distribution of bottom simulating reflectors in seismic records. To learn more about gas hydrate systems and their dynamics at passive and active margins, we drilled boreholes with MARUM-MeBo200 seafloor drill rig at areas where geophysical indications for gas hydrates have been detected in the past. Several gas hydrate proxies like negative chloride anomalies in the pore water, cold spots detected by infrared thermal scans on cores, increased resistivity, and lithological parameters clearly showed the presence of hydrates in the drilled sections. However, gas hydrate was not recovered by MeBo most likely because of small crystal sizes which dissociated during recovery from the seafloor. Three holes were drilled at southern summit of Formosa Ridge down to 126 m below seafloor (mbsf) and recovered sediments from which in situ hydrate saturation values were estimated between 1 and 10% at 15–42 mbsf and even higher values of up to 38% below 100 mbsf. The latter are probably related to the sealing effect of carbonate precipitation which occur at 85–95 mbsf directly above the hydrate-enriched layer. Four holes were drilled at Four-Way Closure Ridge where a maximum drilling depth of 143.90 m was reached. Hydrate presence starts in 65 mbsf continuing down-core with a range of 1–29% gas hydrate saturation in fine-grained homogenous clay. An abrupt change to higher gas hydrate saturation values of up to 80% occurs below 109 mbsf where silty and sandy turbidite layers are often intercalated. Such high gas hydrate contents only occur in the sand layers and not in the fine-grained sediments intercalated to the sand deposits.

Description: The "guest exchange"of methane (CH4) by carbon dioxide (CO2) in naturally occurring gas hydrates is seen as a possibility to concurrently produce CH4 and sequester CO2. Presently, process evaluation is based on CH4-CO2 exchange yields of small-or medium-scale laboratory experiments, mostly neglecting mass and heat transfer processes. This work investigates process efficiencies in two large-scale experiments (210 L sample volume) using fully water-saturated, natural reservoir conditions and a gas hydrate saturation of 50%. After injecting 50 kg of heated CO2 discontinuously (E1) and continuously (E2) and a subsequent soaking period, the reservoir was depressurized discontinuously. It was monitored using electrical resistivity, temperature and pressure sensors, and fluid flow and gas composition measurements. Phase and component inventories were analyzed based on mass and volume balances. The total CH4 production during CO2 injection was only 5% of the initial CH4 inventory. Prior to CO2 breakthrough, the produced CH4 roughly equaled dissolved CH4 in the produced pore water, which balanced the volume of the injected CO2. After CO2 breakthrough, CH4 ratios in the released CO2 quickly dropped to 2.0-0.5 vol %. The total CO2 retention was the highest just before the CO2 breakthrough and higher in E1 where discontinuous injection improved the distribution of injected CO2 and subsequent mixed hydrate formation. The processes were improved by the succession of CO2 injection by controlled degassing at stability limits below that of the pure CH4 hydrate, particularly in experiment E2. Here, a more heterogeneous distribution of liquid CO2 and larger availability of free water led to smaller initial degassing of liquid CO2. This allowed for quick re-formation of mixed gas hydrates and CH4 ratios of 50% in the produced gases. The experiments demonstrate the importance of fluid migration patterns, heat transport, sample inhomogeneity, and secondary gas hydrate formation in water-saturated sediments.

Description: Highlights • Geochemical analyses highlight multiple diagenesis processes occurring in the sediment. • Intense methane seepages and organic matter degradation contribute to the sulfate reduction. • Chemical of dissolved and mineral iron species indicate that iron is associated with clay minerals. • In response to seawater intrusion, ion exchange, dissolution and reverse weathering reactions change the composition of clay constituting the sediment. Abstract Pore water and sediment geochemistry in the western Black Sea were investigated on long Calypso piston core samples. Using this type of coring device facilitates the recovery of the thick sediment record necessary to analyze transport-reaction processes in response to the postglacial sea-level rise and intrusion of Mediterranean salt water 9 ka ago, and thus, to better characterize key biogeochemical processes and process changes in response to the shift from lacustrine to marine bottom water composition. Complementary data indicate that organic matter degradation occurs in the upper 15 m of the sediment column. However, sulfate reduction coupled with Anaerobic Methane Oxidation (AOM) is the dominant electron-accepting process and characterized by a shallow Sulfate Methane Transition Zone (SMTZ). Net silica dissolution, total alkalinity (TA) maxima and carbonate peaks are found at shallow depths. Pore water profiles clearly show the uptake of K+, Mg2+ and Na + by, and release of Ca2+ and Sr2+ from the heterogeneous lacustrine sediments, which is likely controlled by chemical reactions of silicate minerals and changes in clay mineral composition. Iron (Fe2+) and manganese (Mn2+) maxima largely coincide with Ca2+ peaks and suggest a close link between Fe2+, Mn2+ and Ca2+ release. We hypothesize that the Fe2+ maxima below the SMTZ result from deep Fe3+ reduction linked to organic matter degradation, either driven by DOC escaping from the shallow sulfate reduction zone or slow degradation of recalcitrant POC. The chemical analysis of dissolved and solid iron species indicates that iron is essentially associated with clay minerals, which suggests that microbial iron reduction is influenced by clay mineral composition and bioavailability of clay mineral-bound Fe(III). Overall, our study suggests that postglacial seawater intrusion plays a major role in shaping redox zonation and geochemical profiles in the lacustrine sediments of the Late Quaternary.

Description: Carbon capture and storage (CCS) is a key technology to reduce carbon dioxide (CO2) emissions from industrial processes in a feasible, substantial, and timely manner. For geological CO2 storage to be safe, reliable, and accepted by society, robust strategies for CO2 leakage detection, quantification and management are crucial. The STEMM-CCS (Strategies for Environmental Monitoring of Marine Carbon Capture and Storage) project aimed to provide techniques and understanding to enable and inform cost-effective monitoring of CCS sites in the marine environment. A controlled CO2 release experiment was carried out in the central North Sea, designed to mimic an unintended emission of CO2 from a subsurface CO2 storage site to the seafloor. A total of 675 kg of CO2 were released into the shallow sediments (~3 m 49 below seafloor), at flow rates between 6 and 143 kg/d. A combination of novel techniques, adapted versions of existing techniques, and well-proven standard techniques were used to detect, characterise and quantify gaseous and dissolved CO2 in the sediments and the overlying seawater. This paper provides an overview of this ambitious field experiment. We describe the preparatory work prior to the release experiment, the experimental layout and procedures, the methods tested, and summarise the main results and the lessons learnt.

Description: Evaluation of seismic reflection data has identified the presence of fluid escape structures cross-cutting overburden stratigraphy within sedimentary basins globally. Seismically-imaged chimneys/pipes are considered to be possible pathways for fluid flow, which may hydraulically connect deeper strata to the seabed. These fluid migration pathways through the overburden must be constrained to enable secure, long-term subsurface carbon dioxide (CO2) storage. We have investigated a site of natural active fluid escape in the North Sea, the Scanner Pockmark Complex, to determine the physical characteristics of focused fluid conduits, and how they control fluid flow. Here we show that a multi-scale, multi disciplinary experimental approach is required for complete characterisation of fluid escape structures. Geophysical techniques are necessary to resolve fracture geometry and subsurface structure (e.g., multifrequency seismics) and physical parameters of sediments (e.g., controlled source electromagnetics) across length scales (m to km). At smaller (mm to cm) scales, sediment cores were sampled directly and their physical and chemical properties assessed using laboratory-based methods. Numerical modelling approaches bridge the resolution gap, though their validity is dependent on calibration and constraint from field and laboratory experimental data. Further, time-lapse seismic and acoustic methods capable of resolving temporal changes are key for determining fluid flux. Future optimisation of experiment resource use may be facilitated by the installation of permanent seabed infrastructure, and replacement of manual data processing with automated workflows. This study can be used to inform measurement, monitoring and verification workflows that will assist policymaking, regulation, and best practice for CO2 subsurface storage operations.

Description: Highlights • A biogeochemical baseline of sediment geochemistry at potential offshore CCS sites. • Diagnostic indicators of CO2 leakage based on stoichiometry of porewater chemistry. • Porewater chemistry is modified by reverse weathering processes at Goldeneye site. Abstract Injection of carbon dioxide (CO2) into subseafloor reservoirs is gaining traction as a strategy for mitigating anthropogenic CO2 emissions to the atmosphere. Yet, potential leakage, migration and dissolution of externally-supplied CO2 from such reservoirs are a cause for concern. The potential impact of CO2 leakage on the biogeochemistry of sediments and overlying waters in the North Sea was studied during a controlled subsurface CO2 release experiment in 2019 at a potential carbon capture and storage site (Goldeneye). This study describes the natural (unperturbed) biogeochemistry of sediments. They are classified as muddy sand to sandy mud with low organic carbon content (∼0.6 %). Distributions of dissolved inorganic carbon (DIC) and total alkalinity (TA) in sediment porewaters are reported in addition to in situ benthic fluxes of dissolved nutrients and oxygen between the sediments and the overlying water. Oxygen fluxes into the sediment, measured using benthic chambers and eddy covariance, were 6.18 ± 0.58 and 5.73 ± 2.03 mmol m−2 d-1, respectively. Diagnostic indicators are discussed that could be used to detect CO2 enrichment of sediments due to reservoir leakage at CCS sites. These include the ratio TA and ammonium to sulfate in sediment porewaters, benthic fluxes and chloride-normalized cation distributions. These indicators currently suggest that the organic carbon at Goldeneye has an oxidation state below zero and is mainly degraded via sulfate reduction. Carbonate precipitation is apparently negligible, whereas decreases in Mg2+ and K+ point toward ongoing alteration of lithogenic sediments by reverse weathering processes.

Description: Recent studies have begun to explore the potential of enhanced benthic weathering (EBW) in the Baltic Sea as a measure for climate change mitigation. To augment the understanding of EBW under seasonally changing conditions, this study aims to investigate weathering processes under anoxia to hypoxia in corrosive bottom waters, which reflect late summer conditions in the Baltic Sea. Dunite and calcite were added to sediment cores retrieved from Eckernförde Bay (Western Baltic Sea) with a constant flow-through of deoxygenated, CO 2 -enriched Baltic Sea bottom water. The addition of both materials increased benthic alkalinity release by 2.94 μmol cm −2 d −1 (calcite) and 1.12 μmol cm −2 d −1 (dunite), compared to the unamended control experiment. These excess fluxes are significantly higher than those obtained under winter conditions. The comparison with bottom water oxygen concentrations emphasizes that highest fluxes of alkalinity were associated with anoxic phases of the experiment. An increase in Ca and Si fluxes showed that the enhanced alkalinity fluxes could be attributed to calcite and dunite weathering. First order rate constants calculated based on these data were close to rates published in previous studies conducted under different conditions. This highlights the suitability of these proxies for mineral dissolution and justifies the use of these rate constants in modeling studies investigating EBW in the Baltic Sea and areas with similar chemical conditions. Generally stable pH profiles over the course of the experiment, together with the fact that the added minerals remained on the sediment surface, suggest that corrosive bottom waters were the main driving factor for the dissolution of the added minerals. These factors have important implications for the choice of mineral and timing for EBW as a possible marine carbon dioxide removal method in seasonally hypoxic to anoxic regions of the Baltic Sea.