Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

(Table 1) Composition of paraffin hydrocarbons at DSDP Site 56-434

Geochemical investigation of 18 samples of sediments from Site 434 involved determining the content of organic carbon, of bitumoid A (The chloroform A-chl and alcohol-benzene A-alb extracts) and its various fractions, and of individual hydrocarbons as well as the structural group composition of resins. We identified certain samples that differed sharply from the rest by their increased bitumen content and relatively low molecular hydrocarbons and by the fact that their resinous components were more neutral and aliphatic in composition. The distribution of bitumoid and its components seems to reflect migration processes in operation during the early stages of the transformation of organic matter.

Concentration of organic compounds in the snow-ice cover of the Eastern Antarctic

This paper presents data on concentrations and composition of organic substances, lipids, and hydrocarbons, in the snow-ice cover of fast ices and continental lakes of Antarctic. It was shown that organic compounds were accumulated in layers with the most intense autochthonous processes (mainly at the snow-ice and ice-water boundaries). These zones remain active at a biogeochemical medium even at low temperatures. The maximum content of organic compounds (10-20 times that of the snow-ice cover of other regions) and a sharp change in the proportions of their migration forms in the ice volume were detected in the regions of penguin colonies (fast ice in the Buromsky Island and a lake in the Haswell Island). Contents and composition of hydrocarbons in Antarctic ices were compared with those of Arctic ices.

Structural group composition of low-polarity organic matter dissolved in waters of the Northwest Indian Ocean and the Red Sea

Data on amounts of various functional groups, i.e. aldehyde, acid, ester, alcohol, thiol and aromatic groups in several fractions of low-polarity dissolved organic matter are presented. An assumption that this organic matter is part of the lipid fraction is not confirmed. Amount of aromatic compounds in waters of the Northwest Indian Ocean is estimated to be about 1000 times higher than quantity of aromatic hydrocarbons discharged into the ocean each year in petroleum and petroleum products.

Lipids in ocean particulate matter and bottom sediments

Lipid contents both in particulate matter and bottom sediments decreases with passage from the shelf toward the open ocean. Lipid concentration in particulate matter collected by a separator (Ls) decreases by a factor of 7 (from 7.05 to 0.95 % of dry matter), while in particulate matter collected on filters (Lf) it decreases by a factor of 13 (from 78 to 6 µg/l) in the vicinity of the Limpopo River and by a factor of 6 (from 74 to 13 µg/l) in the vicinity of the Zambezi River. Concentration of Lf also decreased with depth. In the upper sediment layers lipid concentration was 0.0028-0.039% of dry matter; all mud samples were richer in lipids, than sand samples. During sedimentogenesis there is an increase in proportion of lipids relative to other classes of organic matter, proportion of low-polarity compounds increases among the lipids, and proportion of hydrocarbons rises among these compounds. Sediments inherit composition of particulate matter to the greatest degree in the vicinity of river mouths.

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Concentrations of organic compounds in suspended matter from surface waters and surface layer bottom sediments of the Obskay Guba (Ob River estuary) and the Kara Sea

Data are presented on concentrations of aliphatic and polycyclic aromatic hydrocarbons (AHC and PAH) in interstitial waters and bottom sediments of the Kara Sea compared to distribution of particulate matter and organic carbon. It was found that AHC concentrations within the water mass (aver. 16 µg/l) are mainly formed by natural processes. Distribution of AHC represents variability of hydrological and sedimentation processes in different regions of the sea. The widest ranges of the concentrations occurred in the Obskaya Guba - Kara Sea section: in water (10-310 µg/l for AHC and 0.4-7.2 ng/l for PAH) and in the surface layer of the bottom sediments (8-42 µg/l for AHC and 9-94 ng/g for PAH). Differentiation of hydrocarbons (HC) in different media follows regularities typical for marginal filters; therefore no oil and pyrogenic compounds are supplied to the open sea. In sediments contents of HC depend on variations in redox conditions in sediments and on their composition.

Organic compounds in snow, ice, and sub-ice waters from the mouth of the Severnaya Dvina River and the Kandalaksha Gulf (White Sea)

The paper reports data on concentrations of organic compounds (organic carbon, lipids; aliphatic hydrocarbons, and polycyclic aromatic hydrocarbons) in snow, ice, and sub-ice waters from the mouth of the Severnaya Dvina River in March 2005-2007 and the Kandalaksha Gulf (Chupa Bay) in March 2004. It was established that organic compounds are accumulated in snow and the upper ice layer near Archangelsk city. Distribution of molecular markers indicates that pollutions were mainly caused by local fallouts. In the Chupa Bay organic compounds are concentrated in the lower ice layer; it is typical for Arctic snow-ice cover. High contents of organic compounds in the snow-ice cover of the White Sea are caused by pollution of air and water during the winter season.

Concentration of organic compounds in slush, under-ice water, and the snow-ice fast-ice cover of the southeast sector of the Antarctic in April 2008

Data are presented on concentration of hydrocarbons (HC) relative to concentrations of suspended matter, lipids, organic carbon, and chlorophyll a in surface waters and snow-ice cover of the East Antarctic coastal areas. It was shown that growth of concentrations of aliphatic HC (AHC) to 30 µg/l in surface waters takes place in frontal zones and under young ice formation. AHC concentration in snow increases with growth of aerosol concentration in the atmosphere. In the lower part of ice, at the boundary with seawater, despite low temperatures, autochthonous processes may provide high AHC concentrations (up to 289 µg/l). Within the snow-ice cover on fast ice, concentration co-variations of all the compounds considered take place.