Carbon isotopic composition and dissolved CO2 concentration in pore waters of ODP Leg 174A sites

Microbially mediated redox diagenetic processes in marine sediments are reflected in the amount and carbon isotopic composition of dissolved CO2 and CH4 (Claypool and Kaplan, 1974). Oxidation of organic matter gives rise to dissolved CO2 with about the same 13C/12C ratio as the starting organic matter. Subsequent reduction of CO2 to form CH4 involves a large (~70) kinetic isotopic effect, resulting in significant 13C depletion in the CH4, and 13C enrichment in the residual CO2. Ocean Drilling Program Leg 174A (offshore New Jersey) presented an opportunity to study these processes in shelf and upper slope sediments. Holes 1071A-1071D, 1071F, and 1072A were drilled on the shelf in water depths of 88.0-98.1 m. Hole 1073A was drilled on the slope in 639.4 m of water. Pore-water samples were collected for analysis at all three sites, whereas gas samples could only be obtained from Hole 1073A on the slope.

Isotopic ratios of methane, ethane, carbon dioxide, inorganic carbon and organic matter from ODP Leg 164 sites

The isotopic characteristics of CH4 (d13C values range from -101.3 per mil to -61.1 per mil PDB, and dD values range from -256 per mil to -136 per mil SMOW) collected during Ocean Drilling Program (ODP) Leg 164 indicate that the CH4 was produced by microbial CO2 reduction and that there is not a significant contribution of thermogenic CH4 to the sampled sediment gas from the Blake Ridge. The isotopic values of CO2 (d13C range -20.6 per mil to +1.24 per mil PDB) and dissolved inorganic carbon (DIC; d13C range -37.7 per mil to +10.8 per mil PDB) have parallel profiles with depth, but with an offset of 12.5 per mil. Distinct downhole variations in the carbon isotopic composition of CH4 and CO2 cannot be explained by closed-system fractionation where the CO2 is solely derived from the locally available sedimentary organic matter (d13C -2.0 per mil ± 1.4 per mil PDB) and the CH4 is derived from CO2 reduction. The observed isotopic profiles reflect the combined effects of upwards gas migration and decreased microbial activity with depth.

C1-C8 hydrocarbons in DSDP Leg 64 Holes sediments

Sediments from the Baja California Continental Margin Transect - Sites 474 and 476 - showed small amounts of C2-C8 hydrocarbons and functionalized compounds (alkenes) typical of organic-rich, Recent, cold (<30°C) marine sediments. In contrast, some samples from Sites 477, 478, 479, and Hole 481A in the Guaymas Basin, an active spreading center, showed the characteristics of thermally generated hydrocarbons. These include an increase (sometimes exponential) in amount and diversity of C2-C8 hydrocarbons and a decrease in alkenes in more thermally mature sediments. The results indicate that the injection of basaltic sills has minimal effect on C2-C8 hydrocarbon generation except in the immediate vicinity of the sill. The absence of light hydrocarbons close to the hottest sills suggests that the compounds distill away as they are formed in these areas of very active hydrothermal circulation. A sample of young sediment exposed to very high temperatures (>300°C) from deeper thermal sources at the hottest site, 477, showed a very limited hydrocarbon distribution, including primarily ethane, benzene, and toluene, together with smaller amounts of propane and butane.

Hydrate, ice and quartz content of eight holes of Leg 204

The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis ("Rietveld method") of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.

Pore water acetate and hydrogen, helium and methane gas concentrations in ODP Leg 204 sediments

Acetate and hydrogen concentrations in pore fluids were measured in samples taken at seven sites from southern Hydrate Ridge (SHR) offshore Oregon, USA. Acetate concentrations ranged from 3.17 to 2515 µM. The maximum acetate concentrations occurred at Site 1251, which was drilled on a slope basin to the east of SHR at depths just above the bottom-simulating reflector (BSR) that marks the boundary of gas hydrate stability. Acetate maxima and localized high acetate concentrations occurred at the BSR at all sites and frequently corresponded with areas of gas hydrate accumulation, suggesting an empirical relationship. Acetate concentrations were typically at a minimum near the seafloor and above the sulfate/methane interface, where sulfate-reducing bacteria may consume acetate. Hydrogen concentrations in pressure core samples ranged from 16.45 to 1036 parts per million by volume (ppmv). In some cases, hydrogen and acetate concentrations were elevated concurrently, suggesting a positive correlation. However, sampling of hydrogen was limited in comparison to acetate, so any relationships between the two analytes, if present, were difficult to discern.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Underway CH4 measurements during POSEIDON cruises POS320/1 and POS348

Coastal upwelling regions have been identified as sites of enhanced CH4 emissions to the atmosphere. The coastal upwelling area off Mauritania (NW Africa) is one of the most biologically productive regions of the world's ocean but its CH4 emissions have not been quantified so far. More than 1000 measurements of atmospheric and dissolved CH4 in the surface layer in the upwelling area off Mauritania were performed as part of the German SOPRAN (Surface Ocean Processes in the Anthropocene) study during two cruises in March/April 2005 (P320/1) and February 2007 (P348). During P348 enhanced CH4 saturations of up to 200% were found close to the coast and were associated with upwelling of South Atlantic Central Water. An area-weighted, seasonally adjusted estimate yielded overall annual CH4 emissions in the range from 1.6 to 2.9 Gg CH4. Thus the upwelling area off Mauritania represents a regional hot spot of CH4 emissions but seems to be of minor importance for the global oceanic CH4 emissions.

Pore water methane characteristics and sulphate reduction rates of ODP Leg 164 sediments

Anaerobic methane oxidation (AMO) was characterized in sediment cores from the Blake Ridge collected during Ocean Drilling Program (ODP) Leg 164. Three independent lines of evidence support the occurrence and scale of AMO at Sites 994 and 995. First, concentration depth profiles of methane from Hole 995B exhibit a region of upward concavity suggestive of methane consumption. Diagenetic modeling of the concentration profile indicates a 1.85-m-thick zone of AMO centered at 21.22 mbsf, with a peak rate of 12.4 nM/d. Second, subsurface maxima in tracer-based sulfate reduction rates from Holes 994B and 995B were observed at depths that coincide with the model-predicted AMO zone. The subsurface zone of sulfate reduction was 2 m thick and had a depth integrated rate that compared favorably to that of AMO (1.3 vs. 1.1 nmol/cm**2/d, respectively). These features suggest close coupling of AMO and sulfate reduction in the Blake Ridge sediments. Third, measured d13CH4 values are lightest at the point of peak model-predicted methane oxidation and become increasingly 13C-enriched with decreasing sediment depth, consistent with kinetic isotope fractionation during bacterially mediated methane oxidation. The isotopic data predict a somewhat (60 cm) shallower maximum depth of methane oxidation than do the model and sulfate reduction data.

Gas hydrates of the Gulf of Mexico

Gas hydrates were recovered from eight sites on the Louisiana slope of the Gulf of Mexico. The gas hydrate discoveries ranged in water depths from 530 to 2400 m occurring as small to medium sized (0.5-50 mm) nodules, interspersed layers (1-10 mm thick) or as solid masses (> 150 mm thick). The hydrates have gas:fluid ratios as high as 170:1 at STP, C1/(C2 + C3) ratios ranging from 1.9 to > 1000 and d13C ratios from -43 to -71 per mil. Thermogenic gas hydrates are associated with oil-stained cores containing up to 7% extractable oil exhibiting moderate to severe biodegradation. Biogenic gas hydrates are also associated with elevated bitumen levels (10-700 ppm). All gas hydrate associated cores contain high percentages (up to 65%) of authigenic, isotopically light carbonate. The hydrate-containing cores are associated with seismic "wipeout" zones indicative of gassy sediments. Collapsed structures, diapiric crests, or deep faults on the flanks of diapirs appear to be the sites of the shallow hydrates.

Chemical and isotopic composition of interstitial waters and hydrocarbon composition at ODP Site 184-1146

Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

Chemical composition of bottom waters and interstitial waters from sediments and deposits within and outside the Haakon Mosby submarine mud volcano in the Norwegian Sea

On the base of data of Cruise 40 of R/V Akademik Keldysh features of formation of saline composition of interstitial waters from sediments containing free hydrocarbons (methane) and gas hydrates (CH4 x 6H2O) were considered. Chemical composition of the interstitial waters is presented for three zones of sediments from the Haakon Mosby submarine mud volcano: (1) zone of kettles containing free hydrocarbons, (2) gas hydrate sediments, and (3) periphery of the volcano. Abnormally high concentrations of bromine and especially iodine characteristic of the interstitial and particularly of the oil-field waters were found. Because of a great interest in natural gas hydrates found in marine sediments, we obtained a possibility to supplement scarce of available published data with some new information.