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: Highlights • In-situ temperature measurements were conducted at the Danube deep sea fan. • Operations were performed with the MARUM-MeBo200 seafloor drill rig. • The BSR is located ∼20 m below the current gas hydrate stability zone. • Seismic data suggest presence of shallower BSR-like events. Abstract Coring, geophysical logging, and in-situ temperature measurements were performed with the MARUM-MeBo200 seafloor rig to characterize gas hydrate occurrences in sediments of the Danube deep sea fan, off Romania, Black Sea. The new drilling data showed no evidence for significant gas hydrate saturations within the sediments but the presence of free gas at the depth of the bottom-simulating reflector (BSR). In-situ temperature and core-derived geochemical data suggest that the current base of the gas hydrate stability zone (BGHSZ) is ∼20 m shallower than the BSR. Investigation of the seismic data around the drill sites shows several locations where free gas previously trapped at a former BGHSZ migrated upwards forming a new reflection above the BSR. This shows that the gas hydrate system in the Danube deep sea fan is still responding to climate changes initiated at the end of the last glacial maximum.

Description: Highlights • An artificial CO2 release demonstrated MMV techniques for offshore CCS. • Detection of leakage was demonstrated using acoustic, chemical and physical approaches. • Attribution of leakage was proved possible using artificial and natural tracer compounds. • Leakage quantification was possible using approaches not previously applied to CCS studies. • Non-catastrophic leaks were detected at levels below those that would cause environmental harm. Carbon capture and storage is a key mitigation strategy proposed for keeping the global temperature rise below 1.5 °C. Offshore storage can provide up to 13% of the global CO2 reduction required to achieve the Intergovernmental Panel on Climate Change goals. The public must be assured that potential leakages from storage reservoirs can be detected and that therefore the CO2 is safely contained. We conducted a controlled release of 675 kg CO2 within sediments at 120 m water depth, to simulate a leak and test novel detection, quantification and attribution approaches. We show that even at a very low release rate (6 kg day−1), CO2 can be detected within sediments and in the water column. Alongside detection we show the fluxes of both dissolved and gaseous CO2 can be quantified. The CO2 source was verified using natural and added tracers. The experiment demonstrates that existing technologies and techniques can detect, attribute and quantify any escape of CO2 from sub-seabed reservoirs as required for public assurance, regulatory oversight and emissions trading schemes.

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.