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.

Changes in bottom water corrosiveness and carbonate ion concentrations in the sub-Antarctic Atlantic during the last glacial period

The glacial climate system transitioned rapidly between cold (stadial) and warm (interstadial) conditions in the Northern Hemisphere. This variability, referred to as Dansgaard-Oeschger variability, is widely believed to arise from perturbations of the Atlantic Meridional Overturning Circulation. Evidence for such changes during the longer Heinrich stadials has been identified, but direct evidence for overturning circulation changes during Dansgaard-Oeschger events has proven elusive. Here we reconstruct bottom water [CO3]2- variability from B/Ca ratios of benthic foraminifera and indicators of sedimentary dissolution, and use these reconstructions to infer the flow of northern-sourced deep water to the deep central sub-Antarctic Atlantic Ocean. We find that nearly every Dansgaard-Oeschger interstadial is accompanied by a rapid incursion of North Atlantic Deep Water into the deep South Atlantic. Based on these results and transient climate model simulations, we conclude that North Atlantic stadial-interstadial climate variability was associated with significant Atlantic overturning circulation changes that were rapidly transmitted across the Atlantic. However, by demonstrating the persistent role of Atlantic overturning circulation changes in past abrupt climate variability, our reconstructions of carbonate chemistry further indicate that the carbon cycle response to abrupt climate change was not a simple function of North Atlantic overturning.

Organic geochemistry of late Cenozoic sediments from the eastern subtropical Atlantic

Detailed organic geochemical investigations have been performed on sediment samples from upwelling Site 658 and nonupwelling Sites 657 and 659. The major objective of this study has been the relationship between organic carbon accumulation and paleoclimatic and paleoceanographic conditions in the upwelling area off northwest Africa during late Cenozoic times. The study is based on results from organic carbon, nitrogen, and hydrogen analyses, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry. In general, nonupwelling Sites 657 and 659 are characterized by low organic carbon values of less than 0.5%. At Site 657, four events of high organic carbon deposition (total organic carbon of 1%-3%) occur and represent turbidites and a slump interval. The upper Pliocene to Pleistocene sediments of upwelling Site 658 display high organic carbon contents of 0.5%-4%, with higher contents concentrated in the upper Pliocene. Accumulation rates of organic carbon vary between 0.1 and 0.5 gC/cm-**2/1000 yr, with maximum values between 3.5 and 3.1 Ma. Short-term cyclic ("Milankovitch-type") variations in organic carbon accumulation suggest climate-controlled mechanisms causing these fluctuations. The quality of organic matter at Site 658 is a mixture of kerogen type II and HI, with a dominance of the marine type. This is indicated by high hydrogen-index values of 200-400 mgHC/gC, low C/N ratios of 5-15, atomic H/C ratios of 1.0-1.5, and high amounts of marine macerals (alginite and liptodetrinite). We have estimated paleoproductivity for Sites 658 and 659 based on the amount of marine organic carbon. At open-marine Site 659, mean paleoproductivity varies between 20 and 50 gC/m**2/yr. At Site 658, mean paleoproductivity reaches high values of 160 to 320 gC/m**2/yr, very similar to those recorded in modern upwelling areas. The changes in productivity off northwest Africa are linked to changes in nutrient supply caused by both upwelling and fluvial input. The change from a dominantly humid climate to one characterized by fluctuations between humid and fully arid climates in northwest Africa occurs between 3.1 and 2.45 Ma.

Lignin, phenols, and some chemical elements in aerosols and bottom sediments from the Tropical North Atlantic

A study of composition of biomarkers (lignin and phenols) in aerosols and bottom sediments from the Tropical North Atlantic was carried out. It was shown that organic matter of aerosols was mostly composed of products of terrestrial plants (arboreal fibers, pollen, and spores). Biomarker composition in the aerosols and in the bottom sediments was practically similar, which proved delivery of terrigenous organic matter to the ocean via the atmosphere.

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.