Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

Oxygen and hydrogen isotope ratios of pore waters from ODP sites in the Mediterranean Sea

Pore fluids from two ODP sites at Eastern Mediterranean mud volcanoes have been analyzed for their Cl concentration and their delta18O and deltaD isotopic composition. The Cl data span a wide range of concentrations, from extremely depleted with respect to seawater (as low as 60 mM) at the crest of Milano dome (site 970) to strongly enriched (up to 5.4 M) at Napoli dome (site 971). Chloride enrichment is known to be due to dissolving Messinian evaporites, whereas the source of the low-Cl fluid is deduced from stable isotope data presented here. The isotopic composition of the endmember fluid is found to be +10? for delta18O and -32? for deltaD for low- as well as for high-Cl waters. From this signature it can be concluded that neither gas hydrates nor meteoric water play a significant role in the freshening of the pore water. Several other processes altering the delta18O/deltaD composition of pore waters are discussed and considered to be of only negligible influence. The process characterizing the isotopic composition of the fluid is found to be clay mineral dehydration (mainly smectite-illite transformation), corresponding to a depth range of 3.5-7 km and an elevated temperature of about 120-165°C. A quantitative estimate shows that this reaction is capable of producing the observed extreme Cl depletion.

Heat-flow studies in the Peru Trench subduction zone

New heat-flow values were obtained in the central Peru Trench area during site surveys and drilling of Ocean Drilling Program (ODP) Leg 112 by measuring temperatures with ordinary surface heat-flow probes and in the drill holes and by estimating from bottom-simulating reflectors resulting from gas hydrates. The values determined by these methods are consistent with each other within the limits of error. When combined with existing data, heat-flow distribution from the trench to the coast was delineated. Heat flow is lower than 40 mW/m**2 at the bottom of the trench and 40 to 50 mW/m**2 on the landward slope. The low heat flow at the trench bottom can be explained partly by a high sedimentation rate. Heat flow is variable about where the Mendana Fracture Zone meets the trench. This low heat flow might result from hydrothermal circulation in the fracture zone, which some scientists believe is a new propagating rift. On the landward slope, no significant difference in heat flow is recognized between the northern side and the southern side of the fracture zone, in spite of differences in the age of the subducting plate and the tectonic history. Heat flow on the landward slope may be slightly higher than that in most other subduction zones.

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.

Boron concentrations and isotope ratios of authigenic carbonates from the Oregon margin

Boron contents and boron, carbon and oxygen stable isotopes were determined for authigenic carbonates recovered from Ocean Drilling Program Leg 146, Oregon margin. Carbonate precipitates are the most widespread authigenic phase in the shallow accretionary wedge and carry chemical information about long-term variations in pore fluid origin and flow paths in the Cascadia subduction zone. Drilling the first ridge (toe area including the frontal thrust) and the second ridge (or Hydrate Ridge) of the prism demonstrated different fluid regimes, with higher B contents in the authigenic precipitates at the toe. The delta11B of 18 authigenic precipitates analysed ranges from 13.9 per mil to as high as 39.8 per mil, extending the upper range of previously reported carbonate delta11B values considerably. When related to the delta11B ratio of their parent solutions, these data are characteristic of fluid-related processes in accretionary prisms. Together with delta13C and delta18O, delta11B ratios of the carbonate concretions, nodules and crusts allow one to distinguish between precipitation influenced by (i) seawater, (ii) fluid reservoirs at different depth levels within the accretionary prism and (iii) cage water from dissociated gas hydrates, the latter possibly indicating a fluctuation of the bottom simulating reflector during most recent Earth's history. From this first systematic boron study on authigenic precipitates from an accretionary prism it is suggested that B contents of such carbonate crusts and concretions exceed those reported for other marine carbonates. Given the abundance of such precipitates at convergent margins, they represent a significant B sink in geochemical cycling. Isotopic compositions of the parent fluids to the carbonates mirror B chemistry of modern pore waters from convergent margins. The precipitates carry information of different subduction-related fluid processes over a certain period of time, and hence are a crucial tracer in the investigation of palaeo-fluid flow.

Gridded bathymetry from multibeam echosounder EM120 data of the cruise M72/4 (2007)

Bathymetry based on data recorded during M72-4 between 25.04.2007 and 11.05.2007 in the Black Sea. This main objective of this cruise was to gain better knowledge of the pathways of methane from their point of formation via potential intermediate deposits to the seafloor in order to understand the mechanisms leading to the submarine discharge of methane-rich fluids. Two regional Black Sea targets have been chosen: The Sorokin Trough, with focused seepage through mud volcanoes, and the Dniepr area where active gas venting occurs from very shallow water depths down to at least 1000 m.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Kerch and the eastern Crimea (2011)

Bathymetry based on data recorded during M84-2 between 26.02.2011 and 02.04.2011 in the Black Sea. The aim of the cruise was to investigate the gas hydrate distribution in sediments of the Black Sea by using several coring technics. In addition to the coring activities the installed EM122 and the PARASOUND system were used to detect gas emissions in the water column and to map large areas of possible seep sites.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Georgia (2011)

Bathymetry based on data recorded during M84-2 between 26.02.2011 and 02.04.2011 in the Black Sea. The aim of the cruise was to investigate the gas hydrate distribution in sediments of the Black Sea by using several coring technics. In addition to the coring activities the installed EM122 and the PARASOUND system were used to detect gas emissions in the water column and to map large areas of possible seep sites.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Samsun (2011)

Bathymetry based on data recorded during M84-2 between 26.02.2011 and 02.04.2011 in the Black Sea. The aim of the cruise was to investigate the gas hydrate distribution in sediments of the Black Sea by using several coring technics. In addition to the coring activities the installed EM122 and the PARASOUND system were used to detect gas emissions in the water column and to map large areas of possible seep sites.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Eregli (2011)

We investigated gas bubble emissions at the Don-Kuban paleo-fan in the northeastern Black Sea regarding their geological setting, quantities as well as spatial and temporal variabilities during three ship expeditions between 2007 and 2011. About 600 bubble-induced hydroacoustic anomalies in the water column (flares) originating from the seafloor above the gas hydrate stability zone (GHSZ) at ~700 m water depth were found. At about 890 m water depth a hydrocarbon seep area named "Kerch seep area" was newly discovered within the GHSZ. We propose locally domed sediments ('mounds') discovered during ultra-high resolution bathymetric mapping with an autonomous underwater vehicle (AUV) to result from gas hydrate accumulation at shallow depths. In situ measurements indicated spatially limited temperature elevations in the shallow sediment likely induced by upward fluid flow which may confine the local GHSZ to a few meters below the seafloor. As a result, gas bubbles are suspected to migrate into near-surface sediments and to escape the seafloor through small-scale faults. Hydroacoustic surveys revealed that several flares originated from a seafloor area of about 1 km**2 in size. The highest flare disappeared in about 350 m water depth, suggesting that the released methane remains in the water column. A methane flux estimate, combining data from visual quantifications during dives with a remotely operated vehicle (ROV) with results from ship-based hydroacoustic surveys and gas analysis revealed that between 2 and 87 x 10**6 mol CH4 yr-1 escaped into the water column above the Kerch seep area. Our results show that the finding of the Kerch seep area represents a so far underestimated type of hydrocarbon seep, which has to be considered in methane budget calculations.