Organic geochemistry of sediment samples from Prydz Bay

High molecular weight aliphatic hydrocarbons were extracted from sediments at two sites (741 and 742) drilled during Ocean Drilling Program Leg 119 in Prydz Bay, a major embayment on the continental shelf of East Antarctica. The distributions of n-alkanes and triterpenoid and steroid hydrocarbons suggest that the n-alkanes and steranes are mainly of terrestrial origin and that the hydrocarbons are immature to slightly mature in the Lower Cretaceous sediments and immature to mature in the Tertiary sediments. At Site 741, the Lower Cretaceous depositional sequence, which is generally characterized by immature hydrocarbons, is interrupted by sediment having more mature components, suggesting a change of source during part of Early Cretaceous time. At Site 742, the mature geochemical parameters of a Pliocene sample correlate with results reported elsewhere for Site 739. In all but one of the other Tertiary samples, the geochemical parameters indicate intermediate maturity. The Lower Cretaceous and Pliocene sediments average about 1.9% organic carbon, a value of interest from the point of view of potential sources of petroleum offshore from Antarctica.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Organofacies reconstruction and lipid geochemistry of sediments from the Galicia margin

Samples of Lower to middle Cretaceous rocks from ODP Sites 638, 640, and 641, drilled on the Galicia continental margin in the northeast Atlantic, have been investigated by organic geochemical methods (i.e., organic carbon determination, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry) to define the Organofacies types and the depositional environments of these sediments. The results of this study fit well into the general picture drawn for the depositional history of the organic matter in Cretaceous organic-carbon-rich sediments in the North Atlantic from previous DSDP investigations. During the Valanginian to Albian, terrigenous organic carbon dominated the organic matter deposited on the Galicia continental margin. Cyclic changes in total organic carbon content were probably controlled by climatic-triggered changes in the supply of terrigenous organic matter from the nearby continent. A drastic change in depositional environment must have occurred near the Cenomanian/Turonian boundary. The preservation of large amounts of marine organic carbon in these sediments was probably caused by anoxic deep-water conditions during that time, rather than high productivity. All of the primary organic matter of the sediment samples investigated is thermally immature, as indicated by very low vitrinite reflectance values.

Composition of swamp waters from the lower Tom' River Basin

New data on chemical and trace component compositions of acidic and low acidic swamp waters and other types of low mineralized waters are reported in the paper. Special attention is paid to dissolved organic compounds: fulvic and humic acids, bitumen, and hydrocarbons. For the first time detailed data on organic trace components (alkanes, pentacyclic terpenoids, steranes, alkylbenzenes, naphthalenes, phenanthrenes, tetraarenes, etc.) in the swamp waters of the Western Siberia: are reported.

Organic geochemistry of lower Cretaceous sediments at DSDP Hole 77-535

At Site 535, the four lithologic units of Cretaceous age are controlled by two types of sedimentologic facies: (1) the massive light-colored limestones or marly limestones in which the total organic carbon (TOC) content is low and the organic matter more or less oxidized and (2) laminated dark facies in which the TOC content is higher and associated with a well-preserved organic matter of Type II origin. Very little typical Type III organic matter occurs in the whole series from late Berriasian to Aptian and Cenomanian. Fluctuations from oxidizing to reducing environments of deposition are proposed to account for the variations in properties of the Type II organic matter between the different facies. Dark laminated layers are good but immature potential source rocks: petroleum potential is often higher than 2 kg HC/t of rock.

Migration of C1 to C8 volatile organic compounds in sediments at DSDP Hole 75-530A

The distribution of C1 to C8 hydrocarbons in sediment samples from DSDP Leg 75, Hole 530A, indicates that significant amounts of methane and ethane have migrated from organic-rich to organic-lean shales in close proximity. Most compounds larger than ethane are not migrating out of black shales, where they occur in high concentrations. These results lead to a general model for assessing migration. In addition, three shale types are identified on the basis of organic carbon and pyrolysis products and patterns.

Analysis of organic matter from DSDP Leg 81 Holes

Organic geochemical and visual kerogen analyses were carried out on approximately 50 samples from Leg 81 (Rockall Plateau, North Atlantic). The sediments are from four sites (Sites 552-555), Pleistocene to Paleocene in age, and represent significantly different depositional environments and sources of organic matter. The Pleistocene glacial-interglacial cycles show differences in sedimentary organic matter based on Rock-Eval pyrolysis, organic phosphorus, and pyrolysis/mass-spectrometry analyses. Glacial samples contain more organic carbon, with a larger proportion of reworked organic matter. This probably reflects increased erosion of continental and shelf areas as a result of low sea level stands. Inter glacial samples contain a larger proportion of marine organic matter as determined by organic phosphorus and pyrolysis analyses. This immature, highly oxidized marine organic matter may be associated with the skeletal organic matrix of calcareous organisms. In addition, Rock-Eval data indicate no significant inorganic-carbonate contribution to the S3 pyrolysis peak. The Pliocene-Miocene sediments consist of pelagic, biogenic carbonates. The organic matter is similar to that of the Pleistocene interglacial periods; a mixture of oxidized marine organic matter and reworked, terrestrial detritus. The Paleocene-Oligocene organic matter reflects variations in source and depositional factors associated with the isolation of Rockall from Greenland. Paleocene sediments contain primarily terrestrial organic matter with evidence of in situ thermal stress resulting from interbedded lava flows. Late Paleocene and early Eocene organic matter suggests a highly oxidized marine environment, with major periods of deposition of terrestrially derived organic matter. These fluctuations in organic-matter type are probably the result of episodic shallowing and deepening of Rockall Basins. The final stage of Eocene/Oligocene sedimentation records the accelerating subsidence of Rockall and its isolation from terrestrial sources (Rockall and Greenland). This is shown by the increasingly marine character of the organic matter. The petroleum potential of sediments containing more than 0.5% organic carbon is poor because of their thermal immaturity and their highly oxidized and terrestrial organic-matter composition.

Organic- and carbonate-carbon values and extract data for DSDP Holes 63-467 and 63-471

Quantity, type, and maturity of the organic matter of middle Miocene to Quaternary sediments from the eastern North Pacific (Deep Sea Drilling Project Leg 63) were determined. Hydrocarbons and fatty acids in lipid extracts were analyzed by capillary column gas chromatography and combined gas chromatography/mass spectrometry. Kerogens were investigated by Rock-Eval pyrolysis and microscopy, and vitrinite reflectance values were determined. At Site 467, in the San Miguel Gap of the outer California Continental Borderland, organic carbon contents range from 1.46% to 5.40%. Normalized to organic carbon, total extracts increase from about 10 to 36 mg/g Corg with depth. The organic matter is a mixture of both marine and terrestrial origin, with the marine organic matter representing a high proportion in some of the samples. Steroid hydrocarbons - sterenes and steradienes in the upper part of the section and steranes in the deepest sample - are the most abundant compounds in the nonaromatic hydrocarbon fractions. Perylene, alkylated thiophenes, and aromatic steroid hydrocarbons dominate in the aromatic hydrocarbon fractions of the shallower samples; increasing maturation is indicated by a more petroleumlike aromatic hydrocarbon distribution. Microscopy revealed a high amount of liptinitic organic matter and confirmed the maturation trend as observed from analysis of the extracts. The vitrinite reflectance may be extrapolated to a bottom-hole value of nearly 0.5% Ro. The liquid hydrocarbon potential of the sediments at higher maturity levels is rated to be good to excellent. At Site 471, off Baja California, organic carbon values are between 0.70% and 1.12%. Extract values increase with depth, as at Site 467. The investigation of the soluble and insoluble organic matter, despite some compositional similarities, consistently revealed a more terrigenous influx compared with Site 467. Thus the potential for liquid hydrocarbon generation is lower, the organic matter being more gas-prone. The deepest sample analyzed indicates the onset of hydrocarbon generation. At this site, frequent sand intercalations offer pathways for migration and possibly reservoir formation.

Petrography and geochemistry of organic matter in Triassic and Cretaceous sediments from the Wombat and Exmouth Plateau

Triassic (Carnian-Rhaetian) continental margin sediments from the Wombat Plateau off northwest Australia (Sites 759, 760, 761, and 764) contain mainly detrital organic matter of terrestrial higher plant origin. Although deposited in a nearshore deltaic environment, little liptinitic material was preserved. The dominant vitrinites and inertinites are hydrogen-lean, and the small quantities of extractable bitumen contain w-alkanes and bacterial hopanoid hydrocarbons as the most dominant single gas-chromatography-amenable compounds. Lower Cretaceous sediments on the central Exmouth Plateau (Sites 762 and 763) farther south in general have an organic matter composition similar to that in the Wombat Plateau sediments with the exception of a smaller particle size of vitrinites and inertinites, indicating more distal transport and probably deposition in deeper water. Nevertheless, organic matter preservation is slightly better than in the Triassic sediments. Long-chain fatty acids, as well as aliphatic ketones and alcohols, are common constituents in the Lower Cretaceous sediments in addition to n-alkanes and hopanoid hydrocarbons. Thin, black shale layers at the Cenomanian/Turonian boundary, although present at several sites (Sites 762 and 763 on the Exmouth Plateau, Site 765 in the Argo Abyssal Plain, and Site 766 on the continental margin of the Gascoyne Abyssal Plain), are particularly enriched in organic matter only at Site 763 (up to 26%). These organic-matter-rich layers contain mainly bituminite of probable fecal-pellet origin. Considering the high organic carbon content, the moderate hydrogen indices of 350-450 milligrams of hydrocarbon-type material per gram of Corg, the maceral composition, and the low sedimentation rates in the middle Cretaceous, we suggest that these black shales were accumulated in an area of oxygen-depleted bottom-water mass (oceanwide reduced circulation?) underlying an oxygen-rich water column (in which most of the primary biomass other than fecal pellets is destroyed) and a zone of relatively high bioproductivity. Differences in organic matter accumulation at the Cenomanian/Turonian boundary at different sites off northwest Australia are ascribed to regional variations in primary bioproductivity.

Biogeochemistry of the Darwin Mounds, NE Atlantic

The Darwin Mounds are a series of small (<=5 m high, 75-100 m diameter) sandy features located in the northern Rockall Trough. They provide a habitat for communities of Lophelia pertusa and associated fauna. Suspended particulate organic matter (sPOM) reaching the deep-sea floor, which could potentially fuel this deep-water coral (DWC) ecosystem, was collected during summer 2000. This was relatively "fresh" (i.e. dominated by labile lipids such as polyunsaturated fatty acids) and was derived largely from phytoplankton remains and faecal pellets, with contributions from bacteria and microzooplankton. Labile sPOM components were enriched in the benthic boundary layer (~10 m above bottom (mab)) relative to 150 mab. The action of certain benthic fauna that are exclusively associated with the DWC ecosystem (e.g. echiuran worms) leads to the subduction of fresh organic material into the sediments. The mound surface sediments are enriched in organic carbon, relative to off-mound sites. There is no evidence for hydrocarbon venting at this location.

Hydrous and anhydrous pyrolysis of DSDP Leg 75 kerogens

The aliphatic hydrocarbon distributions obtained from the natural bitumens of three Leg 75 sediments were compared using computerised gas chromatography-mass spectrometry (C-GC-MS). The kerogens isolated from these sediments were heated in sealed tubes at 330°C using the techniques of hydrous (i.e. heating kerogen in the presence of water) and anhydrous pyrolysis (i.e. heating dry kerogen alone). These experiments were then repeated at a lower temperature (280°C). At 330°C, under anhydrous conditions, considerable destruction of biomarkers in the ancient kerogens (i.e. pre-Tertiary) occurred, whereas with water present significant amounts of hopanes were obtained. However, with more recent kerogens (which contain larger amounts of chemically bound water), both anhydrous and hydrous pyrolysis gave a similar suite of biological markers, in which long chain acyclic isoprenoids (C40) are significant components. Lowering the temperature of pyrolysis to 280°C yielded biological markers under both hydrous and anhydrous conditions for all kerogens. n-Alkenes were not detected in any of the pyrolysates; however, a single unknown triterpene was discovered in several of the hydrous and anhydrous pyrolysates. The results tentatively indicate that the chief value to petroleum research of kerogen hydrous pyrolysis lies in its ability to increase the yield of pyrolysate. High temperature hydrous pyrolysis (280-330°C), under high pressure (2000 psi), does not appear to mimic natural conditions of oil generation. However, this study does not take into account whole rock pyrolysis.

Carbonate, organic carbon and nitrogen, bitumen and rock-eval pyrolysis at DSDP Leg 79 Holes

The lipids and kerogens of 15 sediment samples from Site 547 (ranging from Pleistocene to Early Jurassic/Triassic) and 4 from Site 545 (Cretaceous) have been analyzed. A strong terrestrial contribution of organic matter was found, and significant autochthonous inputs were also present, especially at Site 545. Both strongly reduced and highly oxidized sediments have been found in the Cenozoic and Jurassic samples of Site 547. On the contrary, all the Cretaceous sections of Sites 547 and 545 are anoxic. Sediments from anoxic paleoenvironments are immature and have a high content of sterenes, diasterenes, steradienes, hopenes, and ßß hopanes. Samples from oxic paleoenvironments are mainly mature and their content of hopenes and steriod structures is below the detection level. Nevertheless, their hopane distributions have the immature ßß homologs as the predominant molecular markers. For Site 545 the most abundant molecular markers are ring A monoaromatic steranes, and their presence is attributed to microbial and chemical transformations during early diagenesis.

C1-C7 volatile organic compounds in sediments at DSDP Legs 56-57 Holes

Volatile C1-C7 components in sediments were examined for Japan Trench DSDP Sites 438, 439, 435, 440, 434 and 436, proceeding from west to east. Levels of all components are lowest in the highly fractured sediments of Sites 440 and 434. A number of alkenes, furans, and sulfur compounds were detected in concentrations higher than noted in any other DSDP sediments examined to date. The types, amounts, and specificity of occurrence are similar to those for 1-meter gravity cores we have examined which bear a significant biological imprint. Site 436 shows high levels of saturated and aromatic hydrocarbons, as well as olefins, including traces of dimethycyclopentanes and the highest level of cyclohexene detected in any DSDP sediment we have examined to date. The results from Site 436 were unexpected, considering the low organic-carbon content, absence of biogenic methane, and evidence of an aerobic depositional environment at this site.

Geochemistry of interstitial gases in sedimentary deposits at DSDP Leg 64 Holes

We analyzed interstitial gases from holes at Sites 474, 477, 478, 479, and 481 in the Gulf of California, using gas chromatography and stable isotope mass spectrometry to evaluate their composition in terms of biogenic and thermogenic sources. The hydrocarbon gas (C1-C5) concentrations were comparable to the shipboard data, and no olefins could be detected. The ?13C data for the CH4 confirmed the effects of thermal stress on the sedimentary organic matter, because the values were typically biogenic near the surface and became more depleted in 12C versus depth in holes at Sites 474, 478, and 481. The CH4 at Site 477 was the heaviest, and in Hole 479 it did not show a dominant hightemperature component. The CO2 at depth in most holes was mostly thermogenic and derived from carbonates. The low concentrations of C2-C5 hydrocarbons in the headspace gas of canned sediments precluded a stable carbon-isotope analysis of their genetic origin.