Volume of natural gas within gas-hydrate and free-gas occurrences in ODP Leg 164 sites

Leg 164 of the Ocean Drilling Program was designed to investigate the occurrence of gas hydrate in the sedimentary section beneath the Blake Ridge on the southeastern continental margin of North America. Sites 994, 995, and 997 were drilled on the Blake Ridge to refine our understanding of the in situ characteristics of natural gas hydrate. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas hydrate-bearing sediments. Downhole logging tool strings deployed on Leg 164 included the Schlumberger quad-combination tool (NGT, LSS/SDT, DIT, CNT-G, HLDT), the Formation MicroScanner (FMS), and the Geochemical Combination Tool (GST). Electrical resistivity (DIT) and acoustic transit-time (LSS/SDT) downhole logs from Sites 994, 995, and 997 indicate the presence of gas hydrate in the depth interval between 185 and 450 mbsf on the Blake Ridge. Electrical resistivity log calculations suggest that the gas hydrate-bearing sedimentary section on the Blake Ridge may contain between 2 and 11 percent bulk volume (vol%) gas hydrate. We have determined that the log-inferred gas hydrates and underlying free-gas accumulations on the Blake Ridge may contain as much as 57 trillion m**3 of gas.

Carbon/oxygen ratios, clay composition and gas-hydrate saturation of ODP Leg 164 sites

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Shapefile of the survey tracks of 'Mosaic 02' at the Regab pockmark (Northern Congo Fan)

The Regab pockmark is a large cold seep area located 10 km north of the Congo deep sea channel at about 3160 m water depth. The associated ecosystem hosts abundant fauna, dominated by chemosynthetic species such as the mussel Bathymodiolus aff. boomerang, vestimentiferan tubeworm Escarpia southwardae, and vesicomyid clams Laubiericoncha chuni and Christineconcha regab. The pockmark was visited during the West African Cold Seeps (WACS) cruise with RV Pourquoi Pas? in February 2011, and a 14,000-m**2 high-resolution videomosaic was constructed to map the most populated area and to describe the distribution of the dominant megafauna (mussels, tubeworms and clams). The results are compared with previous published works, which also included a videomosaic in the same area of the pockmark, based on images of the BIOZAIRE cruise in 2001. The 10-year variation of the faunal distribution is described and reveals that the visible abundance and distribution of the dominant megafaunal populations at Regab have not changed significantly, suggesting that the overall methane and sulfide fluxes that reach the faunal communities have been stable. Nevertheless, small and localized distribution changes in the clam community indicate that it is exposed to more transient fluxes than the other communities. Observations suggest that the main megafaunal aggregations at Regab are distributed around focused zones of high flux of methane-enriched fluids likely related to distinct smaller pockmark structures that compose the larger Regab pockmark. Although most results are consistent with the existing successional models for seep communities, some observations in the distribution of the Regab mussel population do not entirely fit into these models. This is likely due to the high heterogeneity of this site formed by the coalescence of several pockmarks. We hypothesize that the mussel distribution at Regab could also be controlled by the occurrence of zones of both intense methane fluxes and reduced efficiency of the anaerobic oxidation of methane possibly limiting tubeworm colonization.

Ocean bottom seismometer sgy-files of refraction seismic profiles from Professor Logachev cruise TTR16/3

Over the last decade pockmarks have proven to be important seabed features that provide information about fluid flow on continental margins. Their formation and dynamics are still poorly constrained due to the lack of proper three dimensional imaging of their internal structure. Numerous fluid escape features provide evidence for an active fluid-flow system on the Norwegian margin, specifically in the Nyegga region. In June-July 2006 a high-resolution seismic experiment using Ocean Bottom Seismometers (OBS) was carried out to investigate the detailed 3D structure of a pockmark named G11 in the region. An array of 14 OBS was deployed across the pockmark with 1 m location accuracy. Shots fired from surface towed mini GI guns were also recorded on a near surface hydrophone streamer. Several reflectors of high amplitude and reverse polarity are observed on the profiles indicating the presence of gas. Gas hydrates were recovered with gravity cores from less than a meter below the seafloor during the cruise. Indications of gas at shallow depths in the hydrate stability field show that methane is able to escape through the water-saturated sediments in the chimney without being entirely converted into gas hydrate. An initial 2D raytraced forward model of some of the P wave data along a line running NE-SW across the G11 pockmark shows, a gradual increase in velocity between the seafloor and a gas charged zone lying at ~300 m depth below the seabed. The traveltime fit is improved if the pockmark is underlain by velocities higher than in the surrounding layer corresponding to a pipe which ascends from the gas zone, to where it terminates in the pockmark as seen in the reflection profiles. This could be due to the presence of hydrates or carbonates within the sediments.

Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Hydrate abundances at the high-flux Batumi seep area in the southeastern Black Sea

Submarine gas hydrates are a major global reservoir of the potent greenhouse gas methane. Since current assessments of worldwide hydrate-bound carbon vary by one order of magnitude, new technical efforts are required for improved and accurate hydrate quantifications. Here we present hydrate abundances determined for surface sediments at the high-flux Batumi seep area in the southeastern Black Sea at 840 m water depth using state-of-the art autoclave technology. Pressure sediment cores of up to 2.65 m in length were recovered with an autoclave piston corer backed by conventional gravity cores. Quantitative core degassing yielded volumetric gas/bulk sediment ratios of up to 20.3 proving hydrate presence. The cores represented late glacial to Holocene hemipelagic sediments with the shallowest hydrates found at 90 cmbsf. Calculated methane concentrations in the different cores surpassed methane equilibrium concentrations in the two lowermost lithological Black Sea units sampled. The results indicated hydrate fractions of 5.2% of pore volume in the sapropelic Unit 2 and mean values of 21% pore volume in the lacustrine Unit 3. We calculate that the studied area of ~ 0.5 km**2 currently contains about 11.3 kt of methane bound in shallow hydrates. Episodic detachment and rafting of such hydrates is suggested by a rugged seafloor topography along with variable thicknesses in lithologies. We propose that sealing by hydrate precipitation in coarse-grained deposits and gas accumulation beneath induces detachment of hydrate/sediment chunks. Floating hydrates will rapidly transport methane into shallower waters and potentially to the sea-atmosphere boundary. In contrast, persistent in situ dissociation of shallow hydrates appears unlikely in the near future as deep water warming by about 1.6 °C and/or decrease in hydrostatic pressure corresponding to a sea level drop of about 130 m would be required. Because hydrate detachment should be primarily controlled by internal factors in this area and in similar hydrated settings, it serves as source of methane in shallow waters and the atmosphere which is mainly decoupled from external forcing.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

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.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.