Stable oxygen isotope ratios, calcium carbonate and opal content in late Pliocene sediments of DSDP Hole 75-532 in the Southeast Atlantic (Table 1)

Site 532 on the Walvis Ridge was sampled at 4000- to 800-year intervals from 2.24 to 2.60 Ma, spanning the three large glacial advances of the late Pliocene. An age model was created by correlating the oxygen isotope record to Site 607 with linear interpolations between tie-lines. The resultant age model differs from that in the site reports by more than 800,000 years, due to misidentification of a magnetic boundary. Sedimentation rates varied by an order of magnitude at this site, with minimum accumulation during glacial events. Interglacial intervals were charactrized by high marine production and high summer precipitation on land, while glacials had very low production and arid continental climate. During the large glacial events (Stages 96-100) conditions of low production and continental aridity reached their greatest intensity, but there is no evidence of a permanent mode shift in either marine or terrestrial records. Calcite concentration has a strong variation at obliquity frequencies, with maxima during interglacials, but occasionally shows a large amplitude at precessional frequencies as well, so that high concentrations occur in a few glacial intervals. As a result, color variation is not a reliable guide to glacial-scale cycles at this site. Composition of the phytoplankton assemblage is diverse and highly variable, and we have not been able to distinguish a clear indicator of upwelling-related production. Spectral analysis reveals obliquity and precessional signals in the pollen data, while several diatom records contain combination tones, indicating that these data represent a complicated response to both local and high-latitude forcing.

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

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.

Hydrous and anhydrous pyrolysis of DSDP Leg 75 kerogens

The aliphatic hydrocarbon distributions obtained from the natural bitumens of three Leg 75 sediments were compared using computerised gas chromatography-mass spectrometry (C-GC-MS). The kerogens isolated from these sediments were heated in sealed tubes at 330°C using the techniques of hydrous (i.e. heating kerogen in the presence of water) and anhydrous pyrolysis (i.e. heating dry kerogen alone). These experiments were then repeated at a lower temperature (280°C). At 330°C, under anhydrous conditions, considerable destruction of biomarkers in the ancient kerogens (i.e. pre-Tertiary) occurred, whereas with water present significant amounts of hopanes were obtained. However, with more recent kerogens (which contain larger amounts of chemically bound water), both anhydrous and hydrous pyrolysis gave a similar suite of biological markers, in which long chain acyclic isoprenoids (C40) are significant components. Lowering the temperature of pyrolysis to 280°C yielded biological markers under both hydrous and anhydrous conditions for all kerogens. n-Alkenes were not detected in any of the pyrolysates; however, a single unknown triterpene was discovered in several of the hydrous and anhydrous pyrolysates. The results tentatively indicate that the chief value to petroleum research of kerogen hydrous pyrolysis lies in its ability to increase the yield of pyrolysate. High temperature hydrous pyrolysis (280-330°C), under high pressure (2000 psi), does not appear to mimic natural conditions of oil generation. However, this study does not take into account whole rock pyrolysis.

Total organic carbon, lithology and alkylthiophenes in immature sediments (Table 1)

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.

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) CaCO3, terrigenous matter and Corg calculations from DSDP Hole 75-532B

Samples taken at 10 cm intervals from DSDP Core 532B-17 contain variations in carbonate, opal, organic carbon, and terrigenous components that correlate with light-dark cycles in sediment color. The core site, at 1300 m water depth, is well above the CCD, yet the color variations appear to result largely from cyclical fluctuations in carbonate dissolution, which was greater during glacial periods. Higher concentrations of organic carbon and of terrigenous sediment components correlate with enhanced carbonate dissolution, but opal concentrations inversely correlate and suggest that biological productivity at this site diminished during glacial periods. A complicated glacial-interglacial picture emerges from the data. In interglacial times, upwelling associated with the Benguela Current produced abundant opaline material, organic matter was fairly well preserved, and carbonate was only moderately dissolved. In glacial times, the upwelling core shifted as sea level fell and winds intensified. Productivity in the waters over Site 532 decreased, but lateral supply of oxidizable organic matter enhanced carbonate dissolution, giving rise to light-dark cycles in these sediments.