Organic geochemistry of Cretaceous black shales

Organic-carbon-rich 'black shales' and adjacent organic-carbon-poor rocks from three different Cretaceous settings encountered during ODP Leg 103 have been studied by organic geochemical methods. Rock-Eval analysis, carbon isotope data, and lipid biomarkers show organic matter to contain varying proportions of marine and continental materials. In Hauterivian-Barremian organic-carbon-rich marlstone turbidites, large amounts of land-derived organic matter are found. Aptian-Albian black-colored shales are interspersed within green claystones, from which they differ by containing more marine organic matter. An abbreviated layer of black shale from the Cenomanian/Turonian boundary is dominated by well-preserved marine organic matter. Downslope transport and rapid reburial within a predominantly oxygenated deep-water setting created most of these examples of black shales, except for the Cenomanian-Turonian deposits in which deep-water anoxia may have been involved.

General descriptions, organic contents and geolipid ratios at DSDP Leg 72 Holes

Organic matter in sediments from Sites 515, 516, and 517 reflects a history of low marine productivity and of oxygenated bottom waters in the western South Atlantic since the Pliocene. Organic carbon contents are low, averaging 0.26% of sediment weight. Distributions of n-alkanes, n-alkanols, and n-alkanoic acids show evidence of microbial reworking, and n-alkanes contain important terrigenous contributions, presumably of eolian origin.

General descriptions, organic contents and ratios of geolipid components at DSDP Holes 75-530B and 75-532

Distributions of free and bound n-alkanes, n-alkanoic acids, and n-alkanols were determined in order to compare the character of organic matter contained in organic-carbon-rich sediments from two sites sampled by the hydraulic piston corer. Two diatomaceous debris-flow samples of Pleistocene age were obtained from Hole 530B in the Angola Basin. A sample of bioturbated Pleistocene diatomaceous clay and another of bioturbated late Miocene nannofossil clay were collected from Hole 532 on the Walvis Ridge. Geolipid distributions of all samples contain large terrigenous contributions and lesser amounts of marine components. Similarities in organic matter contents of Hole 530B and Hole 532 sediments suggest that a common depositional setting, probably on the Walvis Ridge, was the original source of these sediments through Quaternary, and possibly late Neogene, times and that downslope relocation of these biogenic deposits has frequently occurred.

Organic geochemical comparison of Cretaceous green and black claystones at DSDP Hole 75-530A

Three pairs of Upper Cretaceous black shales and adjacent green claystones from Hole 530A were analyzed to compare types and amounts of organic matter and lipids and to seek information about their environments of deposition. The organic-carbon-rich black shales have C/N ratios nearly seven times those of the organic-carbon-lean green claystones. The lipid content of organic matter in the black shales is about ten times less than in adjacent green layers. Organic matter in both types of rocks is thermally immature, and distributions of alkanoic acids, alkanols, sterols, and alkanes contain large amounts of terrigenous components. Pristane/phytane ratios of less than one suggest that younger Turonian sediments were laid down under anoxic conditions, but ratios greater than one suggest that older Turonian Cenomanian deposits accumulated in a more oxic environment. Closely bedded green and black layers have very similar types of lipid distributions and differ primarily in concentrations, although black shales contain somewhat larger amounts of terrigenous lipid components. Geochemical and stratigraphic evidence suggests much of the organic matter in these samples originated on the African continental margin and was transported to the Angola Basin by turbidity flow. Rapid reburial of organic-carbon-rich sediments led to formation of the black shales.

Evolución paleoambiental de la Península Ibérica desde hace 1 Ma a partir de los biomarcadores del registro de la Turbera de Padul (Granada)

La Turbera de Padul, en la Provincia de Granada, ofrece unas posibilidades de estudio muy atractivas desde el punto de vista de la reconstrucción paleoambiental. Se trata de una fosa tectónica subsidente de naturaleza detrítica, a cuyo techo aparecen alternantes niveles de turba. El sondeo, de 107 metros, se realizó en un punto donde los estratos de turba aparecen a mayor profundidad, lo que permite obtener un registro geoquímico orgánico con mucho detalle con una antigüedad de hasta 1Ma. Se tomaron muestras cada 20 cm para el análisis de biomarcadores. Estos biomarcadores se obtuvieron mediante extracción Soxhlet, posterior separación de fracciones de diferente polaridad mediante Cromatografía en Columna, con Gel de Sílice y Alúmina, y posteriormente el análisis e identificación por Cromatografía de Gases - Espectrometría de masas, con confirmación de los compuestos químicos identificados por comparación con Bibliotecas de Espectros de Masas. La datación del sondeo se realizó utilizando distintos métodos como datación por 14C, U/Th, y datación por racemización de aminoácidos. Los resultados dataron el muro del sondeo con una antigüedad de 1 millón de años. El estudio de los biomarcadores ha permitido identificar episodios con distintas características en un escenario complejo, como es la Turbera de Padul, donde el aporte de agua por fusión nival complica la interpretación paleoambiental, y es la responsable de la existencia de la lámina de agua en la turbera en periodos secos con temperaturas elevadas. Se han identificado series de n-alcanos, de n-metilcetonas y series de nalcanoles, que han permitido identificar la aportación de materia orgánica de distintas fuentes al sedimento y por tanto la interpretación paleoambiental. La identificación de diterpenoides fenólicos (cis-Totatol, trans-Totarol y Ferruginol) han permitido identificar episodios de clima templado y húmedo con proliferación de cupresáceas, y precipitaciones abundantes. Por otro lado, se han identificado triterpenoides como el Friedelan-3-ona (Friedelin) y el A-norfriedel-8en-10-ona, cuya relación como precursor (Friedelin) y producto (A-norfriedel-8en-10-ona) ha permitido identificar episodios con fluctuaciones del espesor de la lámina de agua y aporte de material vegetal. ABSTRACT The Bog of Padul, in the province of Granada, offers very attractive possibilities for the study of paleoenvironmental reconstruction. It is a subsiding graben of detrital nature, whose upper part appear alternating peat levels. The core of 107 meters, obtained from a borehole drilled in a place where the layers of peat appear deeper, allowing to obtain organic geochemist information along the last 1 million years. Every 20 cm samples for biomarkers analysis were taken. These biomarkers were obtained by Soxhlet extraction, subsequent separation of fractions of different polarity by column chromatography with silica gel and alumina, and then analyzed and identified by gas chromatography - mass spectrometry, with confirmation of the chemicals identified by comparison to mass spectral libraries. The dating of the core was conducted using different methods such as 14C dating, U/Th, and amino acid racemization dating. The results dated the base of the core to be 1 million years old. The study has identified biomarkers episodes with different characteristics in a complex scenario, such as the Bog of Padul, where the contribution of snowmelt water complicates the paleoenvironmental interpretation, and is responsible for the existence of a sheet of water in dry periods with high temperatures. There have been identified series of n-alkanes, n-methyl ketones and series of n-alkanols that have shown the contribution of different organic matter sources to the sediment and therefore allowed to paleo interpretation. The identification of phenolic diterpenoids (cis-Totatol, trans-Totarol and Ferruginol) have identified episodes of mild and humid climate with proliferation of Cupressaceae, and abundant rainfall. In addition, triterpenoids have been identified, as the friedelan-3-one (friedelin) and the A-norfriedel-8en-10-one, whose relationship as precursor (friedelin) and product (A-norfriedel-8en-10-one) has identified episodes with fluctuations on the thickness of the sheet of water and supply of plant material debris.

Cutin Monomers and Surface Wax Constituents Elicit H2O2 in Conditioned Cucumber Hypocotyl Segments and Enhance the Activity of Other H2O2 Elicitors1

Hypocotyls from etiolated cucumber (Cucumis sativus L.) seedlings were gently abraded at their epidermal surface and cut segments were conditioned to develop competence for H2O2 elicitation. Alkaline hydrolysates of cutin from cucumber, tomato, and apple elicited H2O2 in such conditioned segments. The most active constituent of cucumber cutin was identified as dodecan-1-ol, a novel cutin monomer capable of forming hydrophobic terminal chains. Additionally, the cutin hydrolysates enhanced the activity of a fungal H2O2 elicitor, similar to cucumber surface wax, which contained newly identified alkan-1,3-diols. The specificity of elicitor and enhancement activity was further elaborated using some pure model compounds. Certain saturated hydroxy fatty acids were potent H2O2 elicitors as well as enhancers. Some unsaturated epoxy and hydroxy fatty acids were also excellent H2O2 elicitors but inhibited the fungal elicitor activity. Short-chain alkanols exhibited good elicitor and enhancer activity, whereas longer-chain alkan-1-ols were barely active. The enhancement effect was also observed for H2O2 elicitation by ergosterol and chitosan. The physiological significance of these observations might be that once the cuticle is degraded by fungal cutinase, the cutin monomers may act as H2O2 elicitors. Corrosion of cutin may also bring surface wax constituents in contact with protoplasts and enhance elicitation.

Description of sediments, epoch, calcium carbonate, orgnic carbon, geolipids and mass accumulation rate at DSDP Holes 92-597A, 92-600 and 92-601B

Low concentrations of organic carbon in slowly accumulating sediments from Sites 597, 600, and 601 reflect a history of low marine productivity in the subtropical South Pacific since late Oligocene times. The distributions of n-alkanes, n-alkanoic acids, and n-alkanols provide evidence of the microbial alteration of sediment organic matter. Landderived hydrocarbons, possibly from eolian transport, dominate n-alkane distributions in these samples.

Organic geochemistry from different DSDP Holes in the subtropical South Atlantic Ocean

Organic matter has been characterized in samples of Pleistocene, Pliocene, and Miocene sediments from seven Deep Sea Drilling Project sites in the subtropical South Atlantic Ocean. Organic carbon concentrations average 0.3% for most samples, and n-alkanoic acid, n-alkanol, and alkane biomarkers indicate extensive microbial reworking of organic matter in these organic-carbon-lean sediments. Samples from the easternmost parts of the South Atlantic contain an average of 4.1% organic carbon and reflect the high productivity associated with the Benguela Current. Lipid biomarkers show less microbial reworking in these sediments. Eolian transport of land-derived hydrocarbons is evident at most of these oceanic locations.

(Table 1) Lipid biomarkers in surface sediments from the Gulf of Genoa

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C29 and n-C31 alkanes, n-C26 and n-C28 alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, aeolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C37 alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1 to 30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based UK'37 index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEXH86-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.