Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Sedimentology, mineral magnetism, andoxygen isotope stratigraphy of ODP Hole 133-819A

To investigate late Quaternary paleoclimatic and paleoceanographic change in the sedimentary record, preserved on the Australian Continental Margin during the late Quaternary, core material was collected from Ocean Drilling Program, Leg 133, Site 819. An expanded sequence of late Quaternary, rhythmically bedded, predominantly hemipelagic sediments were recovered from Hole 819A. The foraminiferal d18O record preserved at Hole 819A suggests that the late Quaternary section is incomplete. Both benthic and planktonic d18O stratigraphies can be traced tentatively downcore to stage 6 at about 32.5 mbsf, where a major hiatus occurs. At this level, a slump detachment surface has been identified (Shipboard Scientific Party, 1991). This slump has removed marine oxygen isotope stages 7 to 13. Below 32.5 mbsf, continuous correlation can be achieved in the planktonic d18O curve, with existing deep-sea foraminiferal oxygen isotope stratigraphies from stage 14 through stage 28. The major hiatus at 32.5 mbsf marks the position of a significant change in the character of the sedimentation at Site 819. Sediments below 32.5 mbsf, relative to those above 32.5 mbsf, are characterized by less variation in mean particle size; lower percentages of carbonate content in the coarse fraction (>63 µm); a stronger relationship between the percentage of fine fraction and magnetic mineral concentration, and lower foraminiferal abundances. Above the hiatus, large fluctuations in mean particle size occurred, which have been interpreted to be the result of high foraminiferal abundances. Early highstands show high terrigenous influx in the fine fraction above the hiatus. This is the opposite of the general idea of high terrigenous influx during lowstands of sea level on siliciclastic dominated continental margins. We are far from understanding the origin of this material and further investigation will be required (see also Glenn et al., this volume). All our records, except the planktonic foraminiferal oxygen isotope record, indicate that the major hiatus marks the position of a significant change in the environment at Site 819. The planktonic foraminiferal d18O record suggests that environmental change occurred prior to the formation of the hiatus (i.e., near the Brunhes/Matuyama [B/M] boundary). The interval between the B/M boundary and the hiatus represents a transitional period between two different patterns of ocean circulation. Throughout most of the lower part of the sequence, Site 819 was at a shallow-water depth and local oceanographic conditions were dominated by sluggish Subtropical Central Water (SCW) flow. However, near the B/M boundary, ocean circulation patterns intensified, reflecting a worldwide change in paleoenvironment. Enhanced ocean circulation patterns were possibly aided by tectonic subsidence. During this period Site 819 became progressively more under the influence of Antarctic Intermediate Water (AAIW), than SCW. In the upper part of the sequence at Hole 819 A, we see a continuation of the pattern of oceanographic reorganization suggested during stages 21 through 14. Intensification of the subsurface oceanographic circulation was also accompanied by the progressive wedging southward of surface waters associated with the East Australian Current (EAC). The change in the nature of the records in the lower and upper parts of the sequence at Site 819 are thought to reflect perturbations by the orbital eccentricity cycle.