Description: Hydrocarbon-rich fluids expelled at mud volcanoes (MVs) may contribute significantly to the carbon budget of the oceans, but little is known about the long-term variation in fluid fluxes at MVs. The Darwin MV is one of more than 40 MVs located in the Gulf of Cadiz, but it is unique in that its summit is covered by a thick carbonate crust that has the potential to provide a temporal record of seepage activity. In order to test this idea, we have conducted petrographic, chemical and isotopic analyses of the carbonate crust. In addition a 1-D transport-reaction model was applied to pore fluid data to assess fluid flow and carbonate precipitation at present. The carbonate crusts mainly comprise of aragonite, with a chaotic fabric exhibiting different generations of cementation and brecciation. The crusts consist of bioclasts and lithoclasts (peloids, intraclasts and extraclasts) immersed in a micrite matrix and in a variety of cement types (microsparite, botryoidal, isopachous acicular, radial and splayed fibrous). The carbonates are moderately depleted in 13C (δ13C = − 8.1 to − 27.9‰) as are the pore fluids (δ13C = − 19.1 to − 28.7‰), which suggests that their carbon originated from the oxidation of methane and higher hydrocarbons, like the gases that seep from the MV today. The carbonate δ18O values are as high as 5.1‰, and it is most likely that the crusts formed from 18O-rich fluids derived from dehydration of clay minerals at depth. Pore fluid modelling results indicate that the Darwin MV is currently in a nearly dormant phase (seepage velocities are 〈 0.09 cm yr− 1). Thus, the thick carbonate crust must have formed during past episodes of high fluid flow, alternating with phases of mud extrusion and uplift. Highlights ► Results of pore fluid modelling indicate low seepage activity at localised sites. ► Pore fluids are supersaturated with respect to hydrocarbons of thermogenic origin. ► AOM supports vent fauna and results in the formation of authigenic carbonates. ► The carbonate crust has a brecciated appearance and mainly consists of aragonite. ► The crust formation seems to be regulated by changes in fluid and mudflow activity.

Description: Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment–seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34–180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr−1 at the apex of the MV but they rapidly decrease to 0.4 cm yr−1 at the periphery. The associated fluxes of boron, lithium and methane vary between 7–301, 0.5–6 and 0–806 mmol m−2 yr−1, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.

Description: Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70–80% and up to 30% of C2–C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200–400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Description: We analyse the fluid flow regime within sediments on the Eastern levee of the modern Mississippi Canyon using 3D seismic data and downhole logging data acquired at Sites U1322 and U1324 during the 2005 Integrated Ocean Drilling Program (IODP) Expedition 308 in the Gulf of Mexico. Sulphate and methane concentrations in pore water show that sulphate–methane transition zone, at 74 and 94 m below seafloor, are amongst the deepest ever found in a sedimentary basin. This is in part due to a basinward fluid flow in a buried turbiditic channel (Blue Unit, 1000 mbsf), which separates sedimentary compartments located below and above this unit, preventing normal upward methane flux to the seafloor. Overpressure in the lower compartment leads to episodic and focused fluid migration through deep conduits that bypass the upper compartment, forming mud volcanoes at the seabed. This may also favour seawater circulation and we interpret the deep sulphate–methane transition zones as a result of high downward sulphate fluxes coming from seawater that are about 5–10 times above those measured in other basins. The results show that geochemical reactions within shallow sediments are dominated by seawater downwelling in the Mars-Ursa basin, compared to other basins in which the upward fluid flux is controlling methane-related reactions. This has implications for the occurrence of gas hydrates in the subsurface and is evidence of the active connection between buried sediments and the water column.

Description: Interest in natural gas hydrates has been steadily increasing over the last few decades, with the understanding that exploitation of this abundant unconventional source may help meet the ever-increasing energy demand and assist in reduction of CO2 emission (by replacing coal). Unfortunately, conventional technologies for oil and gas exploitation are not fully appropriate for the specific exploitation of gas hydrate. Consequently, the technology chain, from exploration through production to monitoring, needs to be further developed and adapted to the specific properties and conditions associated with gas hydrates, in order to allow for a commercially and environmentally sound extraction of gas from gas hydrate deposits. Various academic groups and companies within the European region have been heavily involved in theoretical and applied research of gas hydrate for more than a decade. To demonstrate this, Fig. 1.1 shows a selection of leading European institutes that are actively involved in gas hydrate research. A significant number of these institutes have been strongly involved in recent worldwide exploitation of gas hydrate, which are shown in Fig. 1.2 and summarized in Table 1.1. Despite the state of knowledge, no field trials have been carried out so far in European waters. MIGRATE (COST action ES1405) aims to pool together expertise of a large number of European research groups and industrial players to advance gas-hydrate related activity with the ultimate goal of preparing the setting for a field production test in European waters. This MIGRATE report presents an overview of current technologies related to gas hydrate exploration (Chapter 2), production (Chapter 3) and monitoring (Chapter 4), with an emphasis on European activity. This requires covering various activities within different disciplines, all of which contribute to the technology development needed for future cost-effective gas production. The report points out future research and work areas (Chapter 5) that would bridge existing knowledge gaps, through multinational collaboration and interdisciplinary approaches.

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: The Hikurangi Subduction Margin was the recent focus of two IODP expeditions seeking to explore the cause and effect of slow slip earthquake generation at this plate boundary. Characterising the stress field across the Hikurangi Subduction Margin is a crucial element of to understanding the relationship between the contemporary in-situ stress state, active and inactive structures along the subduction front, and fluid pressures and the observed spatial variation in subduction behaviour. Existing stress observations rely on earthquake focal mechanisms and limited onshore borehole data from industry wells on the overriding plate. Reported pore pressures within the over-riding plate are often close to vertical stress magnitudes at shallow depths. Variability of in-situ stress orientations occur along strike of the subduction trench, with a subduction trench parallel SHmax in the south transitioning to a plate motion parallel, trench-oblique SHmax further north. This spatially correlates with observed changes in subduction interface coupling and earthquake behaviour. Here we present new stress field orientation data acquired from resistivity image logging carried out in IODP Expedition 372 using the logging while drilling GeoVision Resistivity tool. We report Shmin orientations from borehole breakout observations of N-S at Site U1518 near the deformation front, and NW-SE from Site U1519 within the upper plate. These data represent the first estimates of stress field orientation (from drilling data) in the outer forarc, near the deformation front of the Hikurangi Margin, an area characterised by shallow slow slip.

Description: Submersible investigations of the Cascadia accretionary complex have identified localized venting of methane gas bubbles in association with gas hydrate occurrence. Acoustic profiles of these bubble plumes in the water column in the vicinity of Hydrate Ridge offshore Oregon provide new constraints on the spatial distribution of these gas vents and the fate of the gas in the water column. The gas vent sites remained active over the span of two years, but varied dramatically on time scales of a few hours. All plumes emanated from local topographic highs near the summit of ridge structures. The acoustic images of the bubble plumes in the water column disappear at water depths between 500 to 460 m, independent of the seafloor depth. This coincides with the predicted depth of the gas hydrate stability boundary of 510 to 490 m, suggesting that the presence of a hydrate skin on the bubble surface prevents them from rapid dissolution. The upper limit of the acoustic bubble plumes at 460 m suggests that dissolution of the residual bubbles is relatively rapid above the hydrate stability zone.

Description: To constrain the fluxes of methane (CH4) in the water column above the accretionary wedge along the Cascadia continental margin, we measured methane and its stable carbon isotope signature (δ13C-CH4). The studies focused on Hydrate Ridge (HR), where venting occurs in the presence of gas-hydrate-bearing sediments. The vent CH4 has a light δ13C-CH4 biogenic signature (−63 to −66‰ PDB) and forms thin zones of elevated methane concentrations several tens of meters above the ocean floor in the overlying water column. These concentrations, ranging up to 4400 nmol L−1, vary by 3 orders of magnitude over periods of only a few hours. The poleward undercurrent of the California Current system rapidly dilutes the vent methane and distributes it widely within the gas hydrate stability zone (GHSZ). Above 480 m water depth, the methane budget is dominated by isotopically heavier CH4 from the shelf and upper slope, where mixtures of various local biogenic and thermogenic methane sources were detected (−56 to −28‰ PDB). The distribution of dissolved methane in the working area can be represented by mixtures of methane from the two primary source regions with an isotopically heavy background component (−25 to −6‰ PDB). Methane oxidation rates of 0.09 to 4.1% per day are small in comparison to the timescales of advection. This highly variable physical regime precludes a simple characterization and tracing of “downcurrent” plumes. However, methane inventories and current measurements suggest a methane flux of approximately 3 × 104 mol h−1 for the working area (1230 km2), and this is dominated by the shallower sources. We estimate that the combined vent sites on HR produce 0.6 × 104 mol h−1, and this is primarily released in the gas phase rather than dissolved within fluid seeps. There is no evidence that significant amounts of this methane are released to the atmosphere locally.