Beschreibung: 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.

Beschreibung: 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.

Beschreibung: Natural gas hydrates are considered a potential resource for gas production on industrial scales. Gas hydrates contribute to the strength and stiffness of the hydrate-bearing sediments. During gas production, the geomechanical stability of the sediment is compromised. Due to the potential geotechnical risks and process management issues, the mechanical behavior of the gas hydrate-bearing sediments needs to be carefully considered. In this study, we describe a coupling concept that simplifies the mathematical description of the complex interactions occurring during gas production by isolating the effects of sediment deformation and hydrate phase changes. Central to this coupling concept is the assumption that the soil grains form the load-bearing solid skeleton, while the gas hydrate enhances the mechanical properties of this skeleton. We focus on testing this coupling concept in capturing the overall impact of geomechanics on gas production behavior though numerical simulation of a high-pressure isotropic compression experiment combined with methane hydrate formation and dissociation. We consider a linear-elastic stress-strain relationship because it is uniquely defined and easy to calibrate. Since, in reality, the geomechanical response of the hydrate-bearing sediment is typically inelastic and is characterized by a significant shear-volumetric coupling, we control the experiment very carefully in order to keep the sample deformations small and well within the assumptions of poroelasticity. The closely coordinated experimental and numerical procedures enable us to validate the proposed simplified geomechanics-to-flow coupling, and set an important precursor toward enhancing our coupled hydro-geomechanical hydrate reservoir simulator with more suitable elastoplastic constitutive models.

Beschreibung: Research and regulations must be integrated to protect seafloor biota from future mining impacts Summary: As human use of rare metals has diversified and risen with global development, metal ore deposits from the deep ocean floor are increasingly seen as an attractive future resource. Japan recently completed the first successful test for zinc extraction from the deep seabed, and the number of seafloor exploration licenses filed at the International Seabed Authority (ISA) has tripled in the past 5 years. Seafloor-mining equipment is being tested, and industrial-scale production in national waters could start in a few years. We call for integrated scientific studies of global metal resources, the fluxes and fates of metal uses, and the ecological footprints of mining on land and in the sea, to critically assess the risks of deep-sea mining and the chances for alternative technologies. Given the increasing scientific evidence for long-lasting impacts of mining on the abyssal environment, precautionary regulations for commercial deep-sea mining are essential to protect marine ecosystems and their biodiversity.

Beschreibung: Current estimates suggest that more than 60% of the global seafloor are covered by millions of abyssal hills and mountains. These features introduce spatial fluid-dynamic granularity whose influence on deep-ocean sediment biogeochemistry is unknown. Here we compare biogeochemical surface-sediment properties from a fluid-dynamically well-characterized abyssal hill and upstream plain: (1) In hill sediments, organic-carbon and -nitrogen contents are only about half as high as on the plain while proteinaceous material displays less degradation; (2) on the hill, more coarse-grained sediments (reducing particle surface area) and very variable calcite contents (influencing particle surface charge) are proposed to reduce the extent, and influence compound-specificity, of sorptive organic-matter preservation. Further studies are needed to estimate the representativeness of the results in a global context. Given millions of abyssal hills and mountains, their integrative influence on formation and composition of deep-sea sediments warrants more attention.

Beschreibung: Takahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well-defined subsurface seismic chimney structure ca. 80,500 m2 in area. Sub-seafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction-transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m−2 yr−1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m−2 yr−1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m−2 yr−1, respectively). A seep-wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation and benthic dissolved methane fluxes of 3.68 × 104 mol yr−1, 73.85 × 104 mol yr−1and 1.19 × 104 mol yr−1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.

Beschreibung: Our study presents a basin-scale 3D modeling solution, quantifying and exploring gas hydrate accumulations in the marine environment around the Green Canyon (GC955) area, Gulf of Mexico. It is the first modeling study that considers the full complexity of gas hydrate formation in a natural geological system. Overall, it comprises a comprehensive basin re-construction, accounting for depositional and transient thermal history of the basin, source rock maturation, petroleum components generation, expulsion and migration, salt tectonics and associated multi-stage fault development. The resulting 3D gas hydrate distribution in the Green Canyon area is consistent with independent borehole observations. An important mechanism identified in this study and leading to high gas hydrate saturation (〉 80 vol. %) at the base of the gas hydrate stability zone (GHSZ), is the recycling of gas hydrate and free gas enhanced by high Neogene sedimentation rates in the region. Our model predicts the rapid development of secondary intra-salt mini-basins situated on top of the allochthonous salt deposits which leads to significant sediment subsidence and an ensuing dislocation of the lower GHSZ boundary. Consequently, large amounts of gas hydrates located in the deepest parts of the basin dissociate and the released free methane gas migrates upwards to recharge the GHSZ. In total, we have predicted the gas hydrate budget for the Green Canyon area that amounts to ∼3,256 Mt of gas hydrate which is equivalent to ∼340 Mt of carbon (∼7 x 1011 m3 of CH4 at STP conditions), and consists mostly of biogenic hydrates.

Beschreibung: The presence of gas hydrates (GHs) increases the stiffness and strength of marine sediments. In elasto‐plastic constitutive models, it is common to consider GH saturation (Sh) as key internal variable for defining the contribution of GHs to composite soil mechanical behavior. However, the stress‐strain behavior of GH‐bearing sediments (GHBS) also depends on the microscale distribution of GH and on GH‐sediment fabrics. A thorough analysis of GHBS is difficult, because there is no unique relation between Sh and GH morphology. To improve the understanding of stress‐strain behavior of GHBS in terms of established soil models, this study summarizes results from triaxial compression tests with different Sh, pore fluids, effective confining stresses, and strain histories. Our data indicate that the mechanical behavior of GHBS strongly depends on Sh and GH morphology, and also on the strain‐induced alteration of GH‐sediment fabrics. Hardening‐softening characteristics of GHBS are strain rate‐dependent, which suggests that GH‐sediment fabrics dynamically rearrange during plastic yielding events. We hypothesize that rearrangement of GH‐sediment fabrics, through viscous deformation or transient dissociation and reformation of GHs, results in kinematic hardening, suppressed softening, and secondary strength recovery, which could potentially mitigate or counteract large‐strain failure events. For constitutive modeling approaches, we suggest that strain rate‐dependent micromechanical effects from alterations of the GH‐sediment fabrics can be lumped into a nonconstant residual friction parameter. We propose simple empirical evolution functions for the mechanical properties and calibrate the model parameters against the experimental data. Plain Language Summary Gas hydrates (GHs) are crystalline‐like solids, which are formed from natural gas molecules and water at high pressure and low temperature. GHs, and particularly methane hydrates, are naturally abundant in marine sediments. It is known that the presence of GH increases the mechanical stiffness and strength of sediments, and there is strong effort in analyzing and quantifying these effects in order to understand potential risks of sediment destabilization or slope failure. Based on our experimental results from high‐pressure geotechnical studies, we show that not only the initial amount and distribution of GH are important for the increased strength of GH‐bearing sediments but also the dynamic rearrangement of GH‐sediment fabrics during deformation characterizes the stress‐strain response and enables strength recovery after failure. We propose that different microstructural mechanisms contribute to this rearrangement and strength recovery of GH sediment. However, we consider these complicated processes in a simplified manner in an improved numerical model, which can be applied for geotechnical risk assessment on larger scales.

Beschreibung: Free gas migration through the gas hydrate stability zone (GHSZ) and subsequent gas seepage at the seabed are characteristic features in marine gas hydrate provinces worldwide. The biogenic or thermogenic gas is typically transported along faults from deeper sediment strata to the GHSZ. Several mechanisms have been proposed to explain free gas transport through the GHSZ. While inhibition of hydrate formation by elevated salinities and temperatures have been addressed previously in studies simulating unfocused, area-wide upward advection of gas, which is not adequately supported by field observations, the role of focused gas flow through chimney-like structures has been underappreciated in this context. Our simulations suggest that gas migration through the GHSZ is, fundamentally, a result of methane gas supply in excess of its consumption by hydrate formation. The required high gas flux is driven by local overpressure, built up from gas accumulating below the base of the GHSZ that fractures the overburden when exceeding a critical pressure, thereby creating the chimney-like migration pathway. Initially rapid hydrate formation raises the temperature in the chimney structure, thereby facilitating further gas transport through the GHSZ. As a consequence, high hydrate saturations form preferentially close to the seafloor, where temperatures drop to bottom water values, producing a prominent subsurface salinity peak. Over time, hydrates form at a lower rate throughout the chimney structure, while initial temperature elevation and salinity peak dissipate. Thus, our simulations suggest that the near-surface salinity peak and elevated temperatures are a result of transient high-flux gas migration through the GHSZ.

Beschreibung: Transport of fluids in gas hydrate bearing sediments is largely defined by the reduction of the permeability due to gas hydrate crystals in the pore space. Although the exact knowledge of the permeability behavior as a function of gas hydrate saturation is of crucial importance, state-of-the-art simulation codes for gas production scenarios use theoretically derived permeability equations that are hardly backed by experimental data. The reason for the insufficient validation of the model equations is the difficulty to create gas hydrate bearing sediments that have undergone formation mechanisms equivalent to the natural process and that have well-defined gas hydrate saturations. We formed methane hydrates in quartz sand from a methane-saturated aqueous solution and used Magnetic Resonance Imaging to obtain time-resolved, three-dimensional maps of the gas hydrate saturation distribution. These maps were fed into 3-D Finite Element Method simulations of the water flow. In our simulations, we tested the five most well-known permeability equations. All of the suitable permeability equations include the term (1-SH)n, where SH is the gas hydrate saturation and n is a parameter that needs to be constrained. The most basic equation describing the permeability behavior of water flow through gas hydrate bearing sand is k = k0 (1-SH)n. In our experiments, n was determined to be 11.4 (±0.3). Results from this study can be directly applied to bulk flow analysis under the assumption of homogeneous gas hydrate saturation and can be further used to derive effective permeability models for heterogeneous gas hydrate distributions at different scales.