Light hydrocarbons in sediments of ODP Site 124-768

Geochemical investigations on gases and interstitial waters from ODP Site 768 (Sulu Trench/Philippines) demonstrate the application of molecular gas composition in combination with stable isotope analyses to the genetic classification of light hydrocarbons. 13C/12C and D/H ratios of methane from gas pockets in cores and gases desorbed from frozen sediments by a vacuum/acid treatment suggest a microbial generation of methane by a CO2 reducing process in sediments with low sulfate concentrations. Isotope data and molecular composition of sediment gases liberated by the vacuum/acid treatment seem to be affected by a secondary desorption process during sampling. A comparison between the D/H ratios of methane from gas pockets and interstitial H2O points to an in-situ generation of methane down to a sub-bottom depth of approx. 720 m. Below this depth hydrogen isotope data indicate a migration of light hydrocarbons into pyroclastic sediments at this site. The occurrence of higher hydrocarbons (propane to pentane) in gases from gas pockets coincides with the vertical distribution of mature organic matter. Gases within the zone of mature organic matter are gases of a mixed microbial and thermal origin.

Isotopic analysis of core gases at DSDP Leg 84 Holes

Methane carbon-isotopic compositions (d13C values relative to the PDB standard) at Sites 565, 566, 567, and 569 were lighter (enriched in 12C) than -60 per mil, indicating a biogenic origin. In the deeper sections at Sites 568 and 570, d13C values were heavier, approaching -40 per mil, and therefore suggest a thermogenic source. A significant thermogenic source was discounted, however, because the carbon dioxide d13C values in these sections were also anomalously heavy, suggesting that the methane may have formed biogenically by reduction of the heavy carbon dioxide. d13C values of ethane and higher hydrocarbons were measured in several sections from Sites 566 and 570 that contained sufficient C2-C4 hydrocarbon concentrations. Ethane values in six sections (245-395 m sub-bottom) from Site 570 were fairly uniform, ranging from -24 to -26 per mil. These values are among the heaviest ethane values reported for natural gases. The isobutane/ n-butane and isopentane/n-pentane ratios of the core gases suggested that the C2-C5 hydrocarbons are thermally produced by low-temperature chemical diagenesis of indigenous organic matter. This process apparently generates isotopically heavy C2-C5 hydrocarbons. High gas concentrations in the serpentinite basement rocks at Sites 566 and 570 appear to have resulted from migrated biogenic methane gas containing small amounts of immature C2-C5 hydrocarbons.

Organic petrography and extractable hydrocarbons of sediments at DSDP Leg 58 Holes

The quantity, type, and maturity of organic matter of Quaternary and Tertiary sediments from the Philippine Sea (DSDP Leg 58; Sites 442-446) were determined. Hydrocarbons in lipid extracts were analyzed by capillary-column gas chromatography. Kerogen concentrates were investigated by microscopy for vitrinite reflectance values and maceral composition. In the Shikoku Basin sediments (Sites 442, 443, and 444), organic carbon values range between 0.03 and 0.44 per cent. The higher values in the younger sediments are interpreted as an indication of increasing deposition of eroded organic particles during the past 4 m.y. Microscopic analyses revealed a dominance of reworked organic matter. Primary material could not be distinguished readily; thus, no maturation trend could be established. Extract yields were low. TV-alkane distributions mostly show maxima at n-C29 and n-C31 and high odd-over-even predominances, typical of material which originated in terrigenous higher plants. The organic-carbon values of sediments of the Daito Ridge and Basin region (Sites 444 and 445) range from less than 0.01 to 0.05 per cent. TV-alkanes exhibit varying marine and terrigenous influences. Some carbonate-rich samples show a pronounced even-over-odd predominance. At least the older sediments contained less recycled organic matter than the Shikoku Basin samples. The maturity, where measurable, was low. None of the Philippine Sea samples indicates a significant hydrocarbon-generation potential.

Lipids and polycyclic aromatic hydrocarbons in bottom sediments from the Atlantic sector of the Southern Ocean

Distribution and composition of lipids and contents of alkanes and polycyclic aromatic hydrocarbons(PAHs) in bottom sediments of the Scotia and Weddell seas are discussed. Comparatively low concentrations of organic carbon (average 0.35%) and lipids (average 0.024%) result from rapid decomposition of organic matter in upper layers of the water column. Composition of alkanes indicates that lipids are of autochthonous origin, and stable concentrations of PAHs (average 25.8 ppb, sigma 15.3 ppb) indicate that they represent the background level for bottom sediments. Higher concentrations of PAHs in sediments near the King George Island (252.1 ppb) and different distributions of individual polyarenes are produced there by the heating systems of the Polish Antarctic Station.

Hydrocarbons, sterols and alkenones at time series station KERFIX

Hydrocarbons, sterols and alkenones were analyzed in samples collected from a 10 month sediment trap time series deployed in the Indian Ocean sector of the Southern Ocean. Fluxes and within-class distributions varied seasonally. During higher mass and organic carbon (OC) flux periods, which occurred in austral summer and fall, fresh marine inputs were predominant. Vertical fluxes were most intense in January, but limited to one week in duration. They were, however, low compared with other oceanic regions. In contrast, low mass and OC flux periods were characterized by a strong unresolved complex mixture (UCM) in the hydrocarbon fraction and a high proportion of stanols as a result of zooplanktonic grazing. Terrigenous inputs were not detectable. The alkenone compositions were consistent with previous data on suspended particles from Antarctic waters. However, UK'37 values diverged from the linear and exponential fits established by Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) in the low temperature range. The seasonal pattern of alkenone production implied that IPT (integrated production temperature) is likely to be strongly imprinted by austral summer and fall SST (sea surface temperature).

Concentrations of aliphatic hydrocarbons and hexachlorocyclohexane isomers in under-ice water, snow, and sea ice from the Greenland Sea

Data on concentrations of aliphatic hydrocarbons and isomers of hexachlorocyclohexane in specimens of various natural environments (water, snow, and ice) of the Greenland Sea obtained during field studies on the ice breaker Otto Shmidt are presented. Analyses were carried out with gas chromatographs using capillary and packed columns. Concentrations of aliphatic and chlorinated hydrocarbons were higher in snow and ice specimens than in sea water and were also higher in less saline water beneath ice. It is concluded that pollutants in this ocean area are at the background level.

Light hydrocarbons in gas pockets and sediments of ODP Site 131-808

A suite of gas samples obtained from gas pockets and sediments of the Nankai accretionary prism (Site 808) has been analyzed for their gas composition and carbon and hydrogen isotope ratios. Gases collected from gas pockets between 10 and 555 mbsf consist of CH4 and CO2. Stable carbon isotope ratios of these two components point to a bacterial formation of methane via CO2-reduction that is also supported by D/H ratios of methane. Methane desorbed from sediments by a vacuum/acid treatment is of bacterial and thermal origin. Mixing between these gas types is indicated by molecular composition and carbon isotope ratios. Diagenetic processes at low temperatures can explain ethane to pentane concentrations from 0 to 850 mbsf. Between 850 mbsf and the basaltic basement hydrocarbon occurrences are related to catagenetic processes at elevated temperatures. Thermal alteration of organic matter is reflected through different gas parameters. Propane carbon isotope values of a sample from the zone of the frontal thrust indicate that the gas likely migrated from sediments of a higher maturity into the immature sediments at 366 mbsf.