Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

Benthic foraminiferal assemblages in ODP Hole 167-1017E

A strong oxygen-minimum zone (OMZ) currently exists along the California margin because of a combination of high surface-water productivity and poor intermediate-water ventilation. However, the strength of this OMZ may have been sensitive to late Quaternary ocean-circulation and productivity changes along the margin. Although sediment-lamination strength has been used to trace ocean-oxygenation changes in the past, oxygen levels on the open margin are not sufficiently low for laminations to form. In these regions, benthic foraminifera are highly sensitive monitors of OMZ strength, and their fossil assemblages can be used to reconstruct past fluctuations. Benthic foraminiferal assemblages from Ocean Drilling Program Site 1017, off Point Conception, exhibit major and rapid faunal oscillations in response to late Quaternary millennial-scale climate change (Dansgaard-Oeschger cycles) on the open central California margin. These faunal oscillations can be correlated to and are apparently synchronous with those reported from Santa Barbara Basin. Together they represent major fluctuations in the strength of the OMZ which were intimately associated with global climate change-weakening, perhaps disappearing, during cool periods and strengthening during warm periods. These rapid, major OMZ strength fluctuations were apparently widespread on the Northeast Pacific margin and must have influenced the evolution of margin biota and altered biogeochemical cycles with potential feedbacks to global climate change.

(Table1) Frequency of well defined bioturbation in sediments of the Eckernförder Bay, Western Baltic Sea

The lamination and burrowing patterns in 17 box cores were analyzed with the aid of X-ray photographs and thin sections. A standardized method of log plotting made statistical analysis of the data possible. Several 'structure types' were established, although it was realized that the boundaries are purely arbitrary divisions in what can sometimes be a continuous sequence. In the transition zone between marginal sand facies and fine-grained basin facies, muddy sediment is found which contains particularly well differentiated, alternating laminae. This zone is also characterized by layers rich in plant remains. The alternation of laminae shows a high degree of statistical scattering. Even though a small degree of cyclic periodicity could be defined, it was impossible to correlate individual layers from core to core across the bay. However, through a statistical handling of the plots, zones could be separated on the basis of the number of sand layers they contained. These more or minder sandy zones clarified the bottom reflections seen in the records of the echograph from the area. The manner of facies change across the bay, suggests that no strong bottom currents are effective in the Eckernförde Bay. The marked asymmetry between the north and south flanks of the profile can be attributed to the stronger action of waves on the more exposed areas. Grain size analyses were made from the more homogeneous units found in a core from the transition-facies zone. The results indicate that the most pronounced differences between layers appear in the silt range, and although the differences are slight, they are statistically significant. Layers rich in plant remains were wet-sieved in order to separate the plant detritus. This was than analyzed in a sediment settling balance and found to be hydrodynamically equivalent to a well-sorted, finegrained sand. A special, rhythmic cross-bedding type with dimensions in the millimeter range, has been named 'Crypto-cross-lamination' and is thought to represent rapid sedimentation in an area where only very weak bottom currents are present. It is found only in the deepest part of the basin. Relatively large sand grains, scattered within layers of clayey-silty matrix, seem to be transported by flotation. Thin section examination showed that the inner part of Eckernförder Bay carbonate grains (e. g. Foraminifera shells) were preserved throughout the cores, while in the outer part of the bay they were not present. Well defined tracks and burrows are relatively rare in all of the facies in comparision to the generally strongly developed deformation burrowing. The application of special measures for the deformation burrowing allowed to plot their intensity in profile for each core. A degree of regularity could be found in these burrowing intensity plots, with higher values appearing in the sandy facies, but with no clear differences between sand and silt layers in the transition facies. Small sections in the profiles of the deepest part of the bay show no bioturbation at all.

(Table 1) Organic and inorganic geochemical analysis of Late Jurassic to Early Cretaceous black shale sediments from the Norwegian-Greenland Seaway

The Late Jurassic to Early Cretaceous (Volgian-Ryazanian) was a period of a second-order sea-level low stand, and it provided excellent conditions for the formation of shallow marine black shales in the Norwegian-Greenland Seaway (NGS). IKU Petroleum Research drilling cores taken offshore along the Norwegian shelf were investigated with geochemical and microscopic approaches to (1) determine the composition of the organic matter, (2) characterize the depositional environments, and (3) discuss the mechanisms which may have controlled production, accumulation, and preservation of the organic matter. The black shale sequences show a wide range of organic carbon contents (0.5-7.0 wt %) and consist of thermally immature organic matter of type II to II/III kerogen. Rock-Eval pyrolysis revealed fair to very good petroleum source rock potential, suggesting a deposition in restricted shallow marine basins. Well-developed lamination and the formation of autochthonous pyrite framboids further indicate suboxic to anoxic bottom water conditions. In combination with very low sedimentation rates it seems likely that preservation was the principal control on organic matter accumulation. However, a decrease of organic carbon preservation and an increase of refractory organic matter from the Volgian to the Hauterivian are superimposed on short-term variations (probably reflecting Milankovitch cycles). Various parameters indicate that black shale formation in the NGS was gradually terminated by increased oxidative conditions in the course of a sea-level rise.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.