Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Organic geochemistry of sediments at DSDP Leg 63 Holes

Selected core samples from the California Continental Borderland (Sites 467-469) were analyzed to evaluate the nature and composition of the lipids and kerogens in terms of their genetic origin and geological maturity. The lipids were of a multiple origin. On the basis of the homolog distributions of the n-alkanes and n-fatty acids, with the shape and magnitude of the unresolved branched and cyclic hydrocarbons, and the structural and stereochemical compositions of the molecular markers, these lipids were derived from primary autochthonous marine (microbial), from allochthonous terrigenous (higher plant wax), and from recycled (geologically mature organic matter) sources. The kerogens were composed of principally marine microbial detritus with a minor input of allochthonous terrestrial material. For the most part, the samples had undergone a thermal maturation according to a normal geothermal gradient, except in the proximity of intrusives. Such additional thermal stress was evident for the samples from Site 469 and to some extent for Site 467 at about a sub-bottom depth of 700 to 800 meters.

Barents and Kara Seas oceanographic data base (BarKode)

Oceanographic data collected by ocean research organisations in Russia, the USA, the United Kingdom, Germany, Norway, and Poland for the Barents, Kara and White Seas region are presented in this atlas. Recently declassified naval data from Norway, the USA, and the UK are also included. More than 1,000,000 oceanographic stations containing temperature and/or sea-water salinity data were originally selected. After correcting errors and eliminating duplicates, data from 206,300 checked stations were placed on CD-ROM, together with many figures describing the characteristics of both the single-input and combined data set. In addition, temperature and salinity measurements were interpolated to the following standard horizons: 0, 25, 50, 100, 150, 200, 250, 300 m, and bottom. This atlas covers the 100-year period 1898 to 1998 and is, to date, the most complete oceanographic data collection for these Arctic shelf seas. This data set is complemented by more than 9,000 measurements of sea surface temperature, which were recently digitized from ships' logbooks. They cover the same geographical area within the time period 1867-1912.

Sedimentology and benthic foraminiferal assemblages of the late Younger Dryas and early Holocene in the Skagerrak

A high-resolution study of palaeoenvironmental changes through the late Younger Dryas and early Holocene in the Skagerrak, the eastern North Atlantic, is based on multi-proxy analyses of core MD99-2286 combined with palaeo-water depth modelling for the area. The late Younger Dryas was characterized by a cold ice-distal benthic foraminiferal fauna. After the transition to the Preboreal (c. 11 650 cal. a BP) this fauna was replaced by a Cassidulina neoteretis dominated fauna, indicating the influence of chilled Atlantic Water at the sea floor. Persisting relatively cold bottom-water conditions until c. 10 300 cal. a BP are presumably a result of an outflow of glacial meltwater from the Baltic area across south-central Sweden, which develops a strong stratification of the water column at MD99-2286. A short-term peak in the C/N ratio at c. 10 200 cal. a BP is suggested to indicate input of terrestrial material, which may represent the drainage of an ice-dammed lake in southern Norway, the Glomma event. After the last drainage route across south-central Sweden closed, c. 10 300 cal. a BP, the meltwater influence diminished, and the Skagerrak resembled a fjord with stable inflow of waters from the North Atlantic through the Norwegian Channel and a gradual increase in boreal species. Full interglacial conditions were established at the sea floor from c. 9250 cal. a BP. Subsequent warm stable conditions were interrupted by a short-term cooling around 8300-8200 cal. a BP, representing the 8.2 ka event.

Global compilation of benthic data sets I

Approaches to quantify the organic carbon accumulation on a global scale generally do not consider the small-scale variability of sedimentary and oceanographic boundary conditions along continental margins. In this study, we present a new approach to regionalize the total organic carbon (TOC) content in surface sediments (<5 cm sediment depth). It is based on a compilation of more than 5500 single measurements from various sources. Global TOC distribution was determined by the application of a combined qualitative and quantitative-geostatistical method. Overall, 33 benthic TOC-based provinces were defined and used to process the global distribution pattern of the TOC content in surface sediments in a 1°x1° grid resolution. Regional dependencies of data points within each single province are expressed by modeled semi-variograms. Measured and estimated TOC values show good correlation, emphasizing the reasonable applicability of the method. The accumulation of organic carbon in marine surface sediments is a key parameter in the control of mineralization processes and the material exchange between the sediment and the ocean water. Our approach will help to improve global budgets of nutrient and carbon cycles.

Accumulation of organic carbon in the Laptev Sea

Composition and accumulation rates of organic carbon in Holocene sediments provided data to calculate an organic carbon budget for the Laptev Sea continental margin. Mean Holocene accumulation rates in the inner Laptev Sea vary between 0.14 and 2.7 g C cm**2/ky; maximum values occur close to the Lena River delta. Seawards, the mean accumulation rates decrease from 0.43 to 0.02 g C cm**2/ky. The organic matter is predominantly of terrigenous origin. About 0.9*10**6 t/year of organic carbon are buried in the Laptev Sea, and 0.25*10**6 t/year on the continental slope. Between about 8.5 and 9 ka, major changes in supply of terrigenous and marine organic carbon occur, related to changes in coastal erosion, Siberian river discharge, and/or Atlantic water inflow along the Eurasian continental margin.

C1-C5 hydrocarbons from core gas pockets at DSDP Leg 56 Holes

C1-C5 hydrocarbons from DSDP Legs 56 and 57 sediment gas pockets were analyzed on board ship. Results suggest that the C2-C5 hydrocarbons accompanied biogenic methane and were generated at low temperatures - less than 50° C - either by microorganisms or by low-temperature chemical reactions. Neopentane, a rare constituent of petroleum, is the major C5 component (about 80%) in much of the sediment at Site 438. This compound, which appeared in smaller amounts at Sites 434, 439, 440, and 441, seems to correlate with either fractured or coarse-grained sediments. Scatter in C4 and C5 isomer ratios and generally good correlation between C3, C4 and C5 components suggest local sources for these molecules.

Geochemical characterizations of the Cretaceous formations at DSDP Holes 93-603B and 11-105

Geochemical characterizations of the Cretaceous formations at Site 603 are quite comparable with those at Site 105. In the Blake-Bahama and the Hatteras formations, the petroleum potential is medium (<5 kg HC/t of rock) to very low (<0.5 kg HC/t of rock), and the organic matter is mainly of type III origin, that is, terrestrial. At the top of the Hatteras Formation, there is a condensed series, which chiefly contains organic matter of type II origin, with up to 20 wt.% total organic carbon content in Core 603B-34 and 25 wt.% in Core 105-9. This accumulation corresponds to the Cenomanian/Turonian boundary event. An examination of dinoflagellates in the kerogen concentration assigns dates to the samples studied by organic geochemistry. The Cenomanian and Turonian age of the organic-matter-rich black claystones indicates a low rate of sedimentation, about 1 m/Ma. Furthermore, the occurrence of type II organic matter indicates an anoxic environment with insufficient oxygen renewal to oxidize the sinking hemipelagic organic matter. This organic enrichment is not related to local phenomena but to sedimentation over an extended area, because deposits are well known in various areas with different paleodepths in the North Atlantic.

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.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.