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.

Geochemistry measured on sediment core GeoB12309-5

Laminated sediment records from the oxygen minimum zone in the Arabian Sea offer unique ultrahigh-resolution archives for deciphering climate variability in the Arabian Sea region. Although numerous analytical techniques are available it has become increasingly popular during the past decade to analyze relative variations of sediment cores' chemical signature by non-destructive X-ray fluorescence (XRF) core scanning. We carefully selected an approximately 5 m long sediment core from the northern Arabian Sea (GeoB12309-5: 24°52.3' N; 62°59.9' E, 956 m water depth) for a detailed, comparative study of high-resolution techniques, namely non-destructive XRF core scanning (0.8 mm resolution) and ICP-MS/OES analysis on carefully selected, discrete samples (1 mm resolution). The aim of our study was to more precisely define suitable chemical elements that can be accurately analyzed and to determine which elemental ratios can be interpretated down to sub-millimeter-scale resolutions. Applying the Student's t-test our results show significantly correlating (1% significance level) elemental patterns for all S, Ca, Fe, Zr, Rb, and Sr, as well as the K/Ca, Fe/Ti and Ti/Al ratios that are all related to distinct lithological changes. After careful consideration of all errors for the ICP analysis we further provide respective factors of XRF Core Scanner software error's underestimation by applying Chi-square-tests, which is especially relevant for elements with high count rates. As demonstrated by these new, ultra-high resolution data core scanning has major advantages (high-speed, low costs, few sample preparation steps) and represents an increasingly required alternative over the time consuming, expensive, elaborative, and destructive wet chemical analyses (e.g., by ICP-MS/OES after acid digestions), and meanwhile also provides high-quality data in unprecedented resolution.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Stable carbon and oxygen isotope compositions of bulk rock samples analyzed from the Zumaia section

Astronomical tuning of sedimentary records to precise orbital solutions has led to unprecedented resolution in the geological time scale. However, the construction of a consistent astronomical time scale for the Paleocene is controversial due to uncertainties in the recognition of the exact number of 405-kyr eccentricity cycles and accurate correlation between key records. Here, we present a new Danian integrated stratigraphic framework using the land-based Zumaia and Sopelana hemipelagic sections from the Basque Basin and deep-sea records drilled during Ocean Drilling Program (ODP) Legs 198 (Shatsky Rise, North Pacific) and 208 (Walvis Ridge, South Atlantic) that solves previous discrepancies. The new coherent stratigraphy utilises composite images from ODP cores, a new whole-rock d13C isotope record at Zumaia and new magnetostratigraphic data from Sopelana. We consistently observe 11 405-kyr eccentricity cycles in all studied Danian successions. We achieve a robust correlation of bioevents and stable isotope events between all studied sections at the ~100-kyr short-eccentricity level, a prerequisite for paleoclimatic interpretations. Comparison with and subsequent tuning of the records to the latest orbital solution La2011 provides astronomically calibrated ages of 66.022 ± 0.040 Ma and 61.607 ± 0.040 Ma for the Cretaceous-Paleogene (K-Pg) and Danian-Selandian 105 (D-S) boundaries respectively. Low sedimentation rates appear common in all records in the mid-Danian interval, including conspicuous condensed intervals in the oceanic records that in the past have hampered the proper identification of cycles. The comprehensive interbasinal approach applied here reveals pitfalls in time scale construction, filtering techniques in particular, and indicates that some caution and scrutiny has to be applied when building orbital chronologies. Finally, the Zumaia section, already hosting the Selandian Global Boundary Stratotype Section and Point (GSSP), could serve as the global Danian unit stratotype in the future.