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.

Organic facies of Cenozoic and Cretaceous sediments at DSDP Leg 80 Holes

The organic facies of Cenozoic sediments cored at DSDP Sites 548-551 along the Celtic Sea margin of the northern North Atlantic (Goban Spur) is dominated by terrestrially derived plant remains and charcoal. Similar organic facies also occur in the Lower and Upper Cretaceous sections at these sites. Mid-Cretaceous (uppermost Albian-Turonian) sediments at Sites 549-551, however, record two different periods of enrichment in organic material, wherein marine organic matter was mixed with terrestrial components. The earlier period is represented only in the uppermost Albianmiddle Cenomanian section at the most seaward site, 550. Here, dark laminated marly chalks rich in organic matter occur rhythmically interbedded with light-colored, bioturbated marly chalks poor in organic matter, suggesting that bottom waters alternated between oxidizing and reducing conditions. A later period of enrichment in organic material is recorded in the upper Cenomanian-Turonian sections at Sites 549 and 551 as a single, laminated black mudstone interval containing biogenic siliceous debris. It was deposited along the margin during a time of oxygen deficiency associated with upwelling-induced intensification and expansion of the mid-water oxygen-minimum layer. In both the earlier and later events, variations in productivity appear to have been the immediate cause of oxygen depletion in the bottom waters.

Geochemistry and pyrolysis at DSDP Hole 77-535

There are substantial differences in the character of organic matter contained in the Pleistocene and Cretaceous sedimentary sequences of DSDP Site 535. The argillaceous Pleistocene section contains type III, gas-prone organic matter whereas the calcareous Cretaceous section is dominated by type II, oil-prone organic matter. A more detailed investigation of the Cretaceous section reveals that the finely laminated limestones of Valanginian to Barremian age are of good to excellent source quality. The indigenous organic matter contained within this organically rich section is thermally immature, not having undergone sufficient thermal diagenesis for the generation and expulsion of hydrocarbons. Within this stratigraphic section, however, staining by mature hydrocarbons was detected. These stains are associated with a fractured interval. These fractures may in turn represent potential migration pathways.

Quantity, provenance, and thermal maturity of organic matter at DSDP Holes 95-612 and 95-613

Using methods of analysis from organic geochemistry and organic petrography, we investigated six Pliocene to Maestrichtian samples from DSDP Site 612 and five Pliocene to Eocene samples from DSDP Site 613 for the quantity, type, and thermal maturity of organic matter. At both sites, organic carbon content is low in the Eocene samples (0.10 to 0.20%) and relatively high in the Pliocene/Miocene samples (0.87 to 1.15%). The Maestrichtian samples from Site 612 contain about 0.6% organic carbon. The organic matter is predominantly terrigenous, as indicated by low hydrogen index values from Rock-Eval pyrolysis and the dominance of long-chain wax alkanes in the extractable hydrocarbons. The organic matter is at a low level of thermal maturity; measured vitrinite reflectance values were between 0.27 and 0.44%.

Organic geochemistry of upper Jurassic-Cretaceous sediments at DSDP Hole 71-511

Cretaceous and Jurassic sediments 435 m thick were drilled at Site 511, in the basin province of the Falkland Plateau, during DSDP Leg 71. The calcareous Unit 3 and the clayey zeolitic Unit 4, both of Senonian age, revealed poorly preserved organic matter indicative of oxidized environments. The same characteristics prevailed for the clayey Unit 5 of Turonian to Albian age. Strictly reducing environments existed for black facies along Unit 6 of earliest Albian to Late Jurassic age and allowed the preservation of a rich organic material that is marine in origin. Besides the transition from reducing conditions in Unit 6 to oxidizing conditions in Unit 5, there are 20 meters of sediments in Cores 56-58 where detrital, nonmarine and then marine organic matter, both implying more or less reducing environments, are interlain by poorly preserved material. In the black shales of the bottom Cores 69 and 70, some nonmarine detritus is mixed with the predominantly marine organic material. An immature stage of evolution can be assigned to all of the samples studied. The chapter also undertakes a comparison with contemporaneous lithologies at adjacent Sites 327 and 330 and attempts some reconstruction of the geography of the eastern Falkland Plateau during the Mesozoic.

Organic geochemical characteristics at DSDP Holes 76-534A and 44-391C

Pyrolysis assay, bitumen analysis, and elemental analysis of kerogen were used to characterize the organic matter of selected core samples from Hole 534A (Leg 76) and Hole 391C (Leg 44) on the Blake-Bahama Plateau. The organic matter throughout the stratigraphic section appears to be principally of a terrestrial origin. The data from several isolated horizons in the Hatteras and Blake-Bahama Formations imply the presence of significant quantities of autochthonous marine organic matter. However, these horizons appear so limited that they cannot be considered potential liquid hydrocarbon source rocks. All the analyzed samples are immature and have not evolved sufficiently to enter into the main stage of hydrocarbon generation. The temporal and spatial restrictions of strata rich in marine organic matter suggest that they do not represent major expansions and contractions of anoxic bottom-water masses, but represent limited occurrences of anoxic conditions.

Organic geochemistry of ODP Leg 135 sediment samples

The average total organic carbon (TOC) content obtained after Rock-Eval/TOC analysis of 156 sediment samples from the eight sites cored during Leg 135 is 0.05%. Hence, the TOC content of Leg 135 sediments is extremely low. The organic matter that is present in these samples is probably mostly reworked and oxidized material. Ten sediment samples were selected for extraction and analysis by gas chromatography and gas chromatography-mass spectrometry. Very low amounts of extractable hydrocarbons were obtained and some aspects of the biomarker distributions suggest that these hydrocarbons are not representative of the organic matter indigenous to the samples. A sample of an oil seep from Pili, Tongatapu was also analyzed. The seep is a biodegraded, mature oil that shows many characteristics in common with previously published analyses of oil seeps from Tongatapu. Biomarker evidence indicates that its source is a mature, marine carbonate of probable Late Cretaceous-Early Tertiary age. The source rock responsible for the Tongatapu oil seeps remains unknown.

Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.

Geochemistry and petrography of organic matter at DSDP Hole 77-535

Organic geochemical and organic petrographic methods were used to study three Lower to middle Cretaceous sediment samples from Hole 535 in the southeastern Gulf of Mexico for organic matter contents and origin and level of maturation. All three samples contain mixed kerogen Type II/III organic matter with a maturity corresponding to about 0.4% vitrinite reflectance. The marine component increases with stratigraphic age, and microbial reworking of the organic matter is significant in each age. The lower two samples of Hauterivian to Valanginian age appear to be impregnated (or contaminated) with soluble polar organic compounds, but there is only a weak indication for the presence of more mature, nonindigenous hydrocarbons.

Mineral nitrogen from KCl extractions of soil from the Jena Experiment (Main Experiment up to 30cm depth, year 2002)

As an estimate of plant-available N, this data set contains measurements of inorganic nitrogen (NO3-N and NH4-N, the sum of which is termed mineral N or Nmin) determined by extraction with 1 M KCl solution of soil samples from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Five soil cores (diameter 0.01 m) were taken at a depth of 0 to 0.15 m and 0.15 to 0.3 m of the mineral soil from each of the experimental plots in September 2002. Samples of the soil cores per plot were pooled during each sampling campaign. NO3-N and NH4-N concentrations were determined by extraction of soil samples with 1 M KCl solution and were measured in the soil extract with a Continuous Flow Analyzer (CFA, Skalar, Breda, Netherlands).

Mineral nitrogen from KCl extractions of soil from the Jena Experiment (Main Experiment up to 30cm depth, year 2004)

As an estimate of plant-available N, this data set contains measurements of inorganic nitrogen (NO3-N and NH4-N, the sum of which is termed mineral N or Nmin) determined by extraction with 1 M KCl solution of soil samples from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Five soil cores (diameter 0.01 m) were taken at a depth of 0 to 0.15 m and 0.15 to 0.3 m of the mineral soil from each of the experimental plots in March and October 2004. Samples of the soil cores per plot were pooled during each sampling campaign. NO3-N and NH4-N concentrations were determined by extraction of soil samples with 1 M KCl solution and were measured in the soil extract with a Continuous Flow Analyzer (CFA, Skalar, Breda, Netherlands).

Mineral nitrogen from KCl extractions of soil from the Jena Experiment (Main Experiment up to 15cm depth, year 2005)

As an estimate of plant-available N, this data set contains measurements of inorganic nitrogen (NO3-N and NH4-N, the sum of which is termed mineral N or Nmin) determined by extraction with 1 M KCl solution of soil samples from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Soil sampling and analysis: Five soil cores (diameter 0.01 m) were taken at a depth of 0 to 0.15 m of the mineral soil from each of the experimental plots in April and September 2005. Samples of the soil cores per plot were pooled during each sampling campaign. NO3-N and NH4-N concentrations were determined by extraction of soil samples with 1 M KCl solution and were measured in the soil extract with a Continuous Flow Analyzer (CFA, Skalar, Breda, Netherlands).

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.