999 resultados para Organic geochemistry


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Based on 13 published porewater H2S and sulphate profiles the amount of H2S escaping from non-bioturbated shales varies between some few % to 45% of the amount of bacterially generated H2S. This finding permits calculation of the original organic carbon (TOCor) content of immature nonbioturbated shales using TOC and sulphur content data. In two immature non-bioturbated sequences from Hungary (Toarcian and Oligocene) the first-order correlation between HI and TOC/TOCor was found to be stronger than that between HI and TOC, indicating that sulphate reduction was the leading process both in decrease in TOC content and degradation of kerogen source potential.

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Soil samples from a Louisiana Barataria Basin brackish marshes were fractionated into acid-volatile sulfides (AVS), HCl-soluble sulfur, elemental sulfur, pyrite sulfur, ester-sulfate sulfur, and carbon-bonded sulfur. Inorganic sulfur composed 13% of total sulfur in brackish marsh soil with HCl-soluble sulfur representing 63–92% of the inorganic sulfur fraction. AVS represented less than 1% of the total sulfur pool. Pyrite sulfur and elemental sulfur together accounted for 8–33% of the inorganic sulfur pool. Organic sulfur, in the forms of ester-sulfate sulfur and carbon-bonded sulfur, was the most dominant pool representing the majority of total sulfur in brackish marsh. Results were compared to values reported for fresh and salt marshes. Reported inorganic sulfur fractions were greater in adjacent marshes, constituting 24% of total sulfur in salt marsh, and 22% in freshwater marshes. Along a salinity gradient, HCl-soluble sulfur represented 78–86% of the inorganic sulfur fraction in fresh, brackish, and salt marsh. Organic sulfur in the forms of ester-sulfate sulfur and carbon-bonded sulfur was the major constituent (76–87%) of total sulfur in all marshes. Reduced sulfur species, except elemental sulfur, increased seaward along the salinity gradient. Accumulation of reduced sulfur forms through sedimentation processes was significant in marsh energy flow in fresh, brackish and salt marshes.

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A series of novel long-chain 3,4-dialkylthiophenes (C36-C54) was identified in a number of sediments ranging from Pleistocene to Cretaceous. The identifications were based on mass spectral characterisation, desulphurisation and mass spectral data of synthesised model compounds. These organic sulphur compounds are probably formed by sulphur incorporation into mid-chain dimethylalkadienes with two methylenic double bonds. These putative precursor lipids are unprecedented and may be considered rather unusual. The distribution of 3,4-dialkylthiophenes in sediments varies considerably with the depositional palaeoenvironment, indicating that these compounds have a potential as molecular markers reflecting changes in palaeoenvironment.

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Detailed petrographical and bulk geochemical investigations of organic matter (OM) have been performed on sediments deposited below or close to upwelling areas offshore Peru (ODP-Leg 112; Sites 679, 681, 688) and Oman (ODP-Leg 117; Sites 720, 723, 724) in order to obtain a quantitative understanding of its accumulation and degradation. Microscopical as well as nanoscopical investigations reveal that the OM in sediments affected by upwelling mechanisms mainly (up to 98%) consists of unstructured (amorphous) organic aggregates without any apparent biological structures. In sediments which are not or to a lesser extent affected by upwelling (Site 720) terrestrial OM predominates. Organic carbon (TOC) contents are highly variable and range between 9.8% in sediments deposited below upwelling cells and 0.2% in sediments outside the upwelling zone. The TOC/sulphur ratios of the sediments scatter widely. The samples from the deep-water locations (Sites 688 and 720), show C/S-ratios of "normal" marine sediments, whereas at the other locations no correlation or even a negative correlation between sulphur and TOC concentration exists. In most of the upwelling-influenced sediments OM contains a significant amount of sulphur. The incorporation of sulphur into the OM followed microbial sulphate reduction and occurred in the upper meters of the sedimentary column. Below, OM is still present in vast amounts and relatively hydrogen-rich, but is nevertheless non-metabolizable and becomes the limiting factor for bacterial sulphate reduction. According to mass balance calculations 90-99% of the OM produced in the photic zone was remineralized and 1-3% was consumed by microbial sulphate reduction. The aerobic and anaerobic processes have greatly affected degradation and conservation of OM.

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Complete records of organic-carbon-rich Cretaceous strata were continuouslycored on the flanks of the Mid-Pacific Mountains and southern Hess Rise in the central North Pacific Ocean during DSDP Leg 62. Organic-carbon-rich laminated silicified limestones were deposited in the western Mid-Pacific Mountains during the early Aptian, a time when that region was south of the equator and considerably shallower than at present. Organic-carbon-rich, laminated limestone on southern Hess Rise overlies volcanic basement and includes 136 m of stratigraphic section of late Albian to early Cenomanian age. This limestone unit was deposited rapidly as Hess Rise was passing under the equatorial high-productivity zone and was subsiding from shallow to intermediate depths. The association of volcanogenic components with organic-carbon-rich strata on Hess Rise in the Mid-Pacific Mountains is striking and suggests that there was a coincidence of mid-plate volcanic activity and the production and accumulation of organic matter at intermediate water depths in the tropical Pacific Ocean during the middle Cretaceous. Pyrolysis assays and analyses of extractable hydrocarbons indicate that the organic matter in the limestone on Hess Rise is composed mainly of lipid-rich kerogen derived from aquatic marine organisms and bacteria. Limestones from the Mid-Pacific Mountains generally contain low ratios of pyrolytic hydrocarbons to organic carbon and low hydrogen indices, suggesting that the organic matter may contain a significant proportion of land-derived material, possibly derived from numerous volcanic islands that must have existed before the area subsided. The organic carbon in all samples analyzed is isotopically light (d13C -24 to -29 per mil) relative to most modern rine organic carbon, and the lightest carbon is also the most lipid-rich. There is a positive linear correlation between sulfur and organic carbon in samples from Hess Rise and from the Mid-Pacific Mountains. The slopes and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts.

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Lipids are used for the evaluation of the different organic matter contributions in the north eastern Norwegian sea (M23258 site; 75ºN, 14ºE) over the last 15,000 years. Development of a mass balance model based on the down core quantification of the C37 alkenones, the odd carbon numbered n-alkanes (Aodd) and the unresolved complex mixture of hydrocarbons (UCM) has allowed three main organic matter inputs involving marine, continental and ancient reworked organic matter to be recognized. The model shows a good agreement between measured and reconstructed TOC values. Similarly, a strong parallelism is observed between predicted components such as marine TOC and carbonate content (CaCO3), which was determined independently. Representation of the model results within a time-scale based on 15 AMS-14C measurements shows that the main changes in organic matter constituents are coincident with the major climatic events of the last 15,000 a. Thus, the predominance of reworked organic matter is characteristic of Termination Ia (up to 70%), continental organic matter was dominant during the Bølling-Allerød (B-A) and Younger Dryas (YD) periods (about 85%) and a strong increase of marine organic matter occurred in the Holocene (between 50 and 75%). This agreement reflects the main hydrographic changes that determined the deposition of sedimentary materials during the period studied: ice-rafted detritus from the Barents continental platform, ice-melting waters from the Arctic fluvial system discharging into the Barents sea and dominance of north Atlantic currents, respectively. In this respect, the high-resolution down core record resulting from the mass balance and lipid measurements allows the identification of millennial-scale events such as the increase of reworked organic matter at the final retreat of the Barents ice sheet at the end of the deglaciation period (Termination Ib).

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Stable carbon and nitrogen isotopic compositions as well as organic carbon and total nitrogen contents are reported for Site 645 in Baffin Bay and Sites 646 and 647 in the Labrador Sea. Both low-resolution analyses (1 sample/section) and high-resolution results (up to 7 samples/section) are presented. These records indicate that large-scale changes in productivity since the middle Miocene have occurred in Baffin Bay. Such changes are not evident in samples from the Labrador Sea. Isotopic records of all the sites are influenced strongly by rapidly changing influxes that combine terrigenous debris with planktonic production. In parts of the cores, relationships to other phenomena, such as ice stages, are present. However, these correlations are not common and indicate that these events were masked by the dynamic changes in sources of organic matter occurring in this complex system.