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.

Gas content, composition of gas hydrate and volumetric gas/water ratios of ODP and DSDP sites

Gas hydrate samples were recovered from four sites (Sites 994, 995, 996, and 997) along the crest of the Blake Ridge during Ocean Drilling Program (ODP) Leg 164. At Site 996, an area of active gas venting, pockmarks, and chemosynthetic communities, vein-like gas hydrate was recovered from less than 1 meter below seafloor (mbsf) and intermittently through the maximum cored depth of 63 mbsf. In contrast, massive gas hydrate, probably fault filling and/or stratigraphically controlled, was recovered from depths of 260 mbsf at Site 994, and from 331 mbsf at Site 997. Downhole-logging data, along with geochemical and core temperature profiles, indicate that gas hydrate at Sites 994, 995, and 997 occurs from about 180 to 450 mbsf and is dispersed in sediment as 5- to 30-m-thick zones of up to about 15% bulk volume gas hydrate. Selected gas hydrate samples were placed in a sealed chamber and allowed to dissociate. Evolved gas to water volumetric ratios measured on seven samples from Site 996 ranged from 20 to 143 mL gas/mL water to 154 mL gas/mL water in one sample from Site 994, and to 139 mL gas/mL water in one sample from Site 997, which can be compared to the theoretical maximum gas to water ratio of 216. These ratios are minimum gas/water ratios for gas hydrate because of partial dissociation during core recovery and potential contamination with pore waters. Nonetheless, the maximum measured volumetric ratio indicates that at least 71% of the cages in this gas hydrate were filled with gas molecules. When corrections for pore-water contamination are made, these volumetric ratios range from 29 to 204, suggesting that cages in some natural gas hydrate are nearly filled. Methane comprises the bulk of the evolved gas from all sites (98.4%-99.9% methane and 0%-1.5% CO2). Site 996 hydrate contained little CO2 (0%-0.56%). Ethane concentrations differed significantly from Site 996, where they ranged from 720 to 1010 parts per million by volume (ppmv), to Sites 994 and 997, which contained much less ethane (up to 86 ppmv). Up to 19 ppmv propane and other higher homologues were noted; however, these gases are likely contaminants derived from sediment in some hydrate samples. CO2 concentrations are less in gas hydrate than in the surrounding sediment, likely an artifact of core depressurization, which released CO2 derived from dissolved organic carbon (DIC) into sediment. The isotopic composition of methane from gas hydrate ranges from d13C of -62.5 per mil to -70.7 per mil and dD of -175 per mil to -200 per mil and is identical to the isotopic composition of methane from surrounding sediment. Methane of this isotopic composition is mainly microbial in origin and likely produced by bacterial reduction of bicarbonate. The hydrocarbon gases here are likely the products of early microbial diagenesis. The isotopic composition of CO2 from gas hydrate ranges from d13C of -5.7 per mil to -6.9 per mil, about 15 per mil lighter than CO2 derived from nearby sediment.

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.

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.

(Table 1) Chemical composition of interstitial waters from the area of gas hydrate generation, Sea of Okhotsk

Distributions of halogens (Cl, Br and I) in interstitial waters from sediments containing methane hydrate and in water of the hydrate itself are presented. High concentrations of halogens do not occur in interstitial waters from sediments that contain gas hydrates. The main reason for their low concentrations is the poverty of organic matter in sediments.

Gas analysis of sediment cores from the Batumi seep area

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone. Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (>99.85 mol.% of Sum[C1-C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] > 1000) and stable isotopic compositions of methane (d13C = -53.5 per mill V-PDB; D/H around -175 per mill SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by >0.03 mol.% (Sum[C1-C4, CO2]) relative to the other gas types and the virtual lack of 14C-CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely. As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% Sum(C1-C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C-CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.

Methane hydrate at DSDP Site 84-570

Deep Sea Drilling Project (DSDP) studies at Site 570 on the landward slope of the Middle America Trench off Guatemala allow for the first time a quantitative estimate of the methane hydrate content in the massive mudstones deposited there. Drilling across the Guatemalan transect on DSDP Legs 67 and 84 has resulted in the greatest number of visual observations of gas hydrate in any marine area. At Site 570, a 1.5-m-long section of massive methane hydrate was unexpectedly cored in an area where none of the usual signs of gas hydrate in seismic records were present. The sediment section is similar to that recovered at the other eight sites off Guatemala, but drilling at Site 570 may have penetrated through a fault zone that provided the space for accumulation of massive gas hydrate. The methane hydrate was analyzed using the following well logs: density, sonic, resistivity, gamma-ray, caliper, neutron porosity, and temperature. The density, sonic, and resistivity logs define a 15-m-thick hydrated zone within which a 4-m-thick nearly pure hydrate section is contained. The methane gas content ranges from 240 m**3 to 1400 m**3 per m**2 of lateral extent; and if the body extends a square kilometer, its total volume of stored gas could be from 240*10**6m**3 to 1400*10**6m**3. Because the acoustic impedance of hydrate calculated from the sonic and density logs shows no anomalous values, the shape and extent of the hydrate body cannot be defined in seismic records. Thus the body is theoretically nonreflective in contrast to the base of the hydrate reflection. The base of the gas hydrate reflection is presumed to be the result of the velocity contrast between sediment containing gas hydrate and sediment containing free gas.