Geochemistry and stratigraphy on sediment cores from Leg198 and Leg 208

The first complete cyclic sedimentary successions for the early Paleogene from drilling multiple holes have been retrieved during two ODP expeditions: Leg 198 (Shatsky Rise, NW Pacific Ocean) and Leg 208 (Walvis Ridge, SE Atlantic Ocean). These new records allow us to construct a comprehensive astronomically calibrated stratigraphic framework with an unprecedented accuracy for both the Atlantic and the Pacific Oceans covering the entire Paleocene epoch based on the identification of the stable long-eccentricity cycle (405-kyr). High resolution X-ray fluorescence (XRF) core scanner and non-destructive core logging data from Sites 1209 through1211 (Leg 198) and Sites 1262, 1267 (Leg 208) are the basis for such a robust chronostratigraphy. Former investigated marine (ODP Sites 1001 and 1051) and land-based (e.g., Zumaia) sections have been integrated as well. The high-fidelity chronology is the prerequisite for deciphering mechanisms in relation to prominent transient climatic events as well as completely new insights into Greenhouse climate variability in the early Paleogene. We demonstrate that the Paleocene epoch covers 24 long eccentricity cycles. We also show that no definite absolute age datums for the K/Pg boundary or the Paleocene - Eocene Thermal Maximum (PETM) can be provided by now, because of still existing uncertainties in orbital solutions and radiometric dating. However, we provide two options for tuning of the Paleocene which are only offset by 405-kyr. Our orbitally calibrated integrated Leg 208 magnetostratigraphy is used to revise the Geomagnetic Polarity Time Scale (GPTS) for Chron C29 to C25. We established a high-resolution calcareous nannofossil biostratigraphy for the South Atlantic which allows a much more detailed relative scaling of stages with biozones. The re-evaluation of the South Atlantic spreading rate model features higher frequent oscillations in spreading rates for magnetochron C28r, C27n, and C26n.

Planktonic foraminiferal oxygen isotopes of ODP Site 143-865 samples

Cool tropical sea surface temperatures (SSTs) are reported for warm Paleogene greenhouse climates based on the d18O of planktonic foraminiferal tests. These results are difficult to reconcile with models of greenhouse gas-forced climate. It has been suggested that this "cool tropics paradox" arises from postdepositional alteration of foraminiferal calcite, yielding erroneously high d18O values. Recrystallization of foraminiferal tests is cryptic and difficult to quantify, and the compilation of robust d18O records from moderately altered material remains challenging. Scanning electron microscopy of planktonic foraminiferal chamber-wall cross sections reveals that the basal area of muricae, pustular outgrowths on the chamber walls of species belonging to the genus Morozovella, contain no mural pores and may be less susceptible to postdepositional alteration. We analyzed the d18O in muricae bases of morozovellids from the central Pacific (Ocean Drilling Program Site 865) by ion microprobe using 10 ?m pits with an analytical reproducibility of ±0.34 per mil (2 standard deviations). In situ measurements of d18O in these domains yield consistently lower values than those published for conventional multispecimen analyses. Assuming that the original d18O is largely preserved in the basal areas of muricae, this new d18O record indicates Early Paleogene (~49-56 Ma) tropical SSTs in the central Pacific were 4°-8°C higher than inferred from the previously published d18O record and that SSTs reached at least ~33°C during the Paleocene-Eocene thermal maximum. This study demonstrates the utility of ion microprobe analysis for generating more reliable paleoclimate records from moderately altered foraminiferal tests preserved in deep-sea sediments.

Documentation of sediment cores during SONNE Expedition SO228 from the western tropical Pacific

The core descriptions (chapter 7) summarize the most important results of the analysis of each sediment core following procedures applied during ODP/IODP expeditions. All cores were opened, described, and color-scanned. In the core descriptions the first column displays the lithological data that are based on visual analysis of the core and are supplemented by information from binocular and smear slide analyses. The sediment classification largely follows ODP/IODP convention. Lithological names consist of a principal name based on composition, degree of lithification, and/or texture as determined from visual description and microscopic observations. In the structure column the intensity of bioturbation together with individual or special features (turbidites, volcanic ash layers, plant debris, shell fragments, etc.) is shown. The hue and chroma attributes of color were determined by comparison with the Munsell soil color charts and are given in the color column in the Munsell notation. A GretagMacbethTM Spectrolino spectrophotometer was used to measure percent reflectance values of sediment color at 36 wavelength channels over the visible light range (380-730 nm) on all of the cores. The digital reflectance data of the spectrophotometer readings were routinely obtained from the surface (measured in 1 cm steps) of the split cores (archive half). The Spectrolino is equipped with a measuring aperture with folding mechanism allowing an exact positioning on the split core and is connected to a portable computer. The data are directly displayed within the software package Excel and can be controlled simultaneously. From all the color measurements, for each core the red/blue ratio (700 nm/450 nm) and the lightness are shown together with the visual core description. The reflectance of individual wavelengths is often significantly affected by the presence of minor amounts of oxyhydroxides or sulphides. To eliminate these effects, we used the red/blue ratio and lightness.

Documentation of Graf-Wilczek-Knoll

During Leg ANT-XXIII/9 on the 31st March 2007 the German research vessel Polarstern mapped a significant bathymetric feature with its swath sonar system at the north-west margin of the Kerguelen Plateau. Due to the fact, that the feature was discovered just a month after the third IPY 2007/2008 has started, it was named after Graf Wilczek who, together with Carl Weyprecht, had promoted the first IPY. The undersea feature name proposal was officialy accepted by the GEBCO Sub-Committee on Undersea Feature Names (SCUFN) at its 20th meeting in late July and was added to the GEBCO Gazetteer of UFN (http://www.iho.shom.fr/COMMITTEES/GEBCO/SCUFN/scufn_intro.htm). ______________ Graf Hans Wilczek (Notation of the name from the book of Wilczek's daughter Elisabeth Kinsky- Wilczek). The Austrian naval hero Tegetthoff in 1871 planned an expedition to the southern hemisphere. The geophysicist G. Neumayer (1826-1909) already was selected as its chief scientist. Also the naval officer Carl Weyprecht (1838-1881) and the mountaineer Julius Payer (1841-1915) were to participate. Because of the sudden death of Tegettoff the project came to a halt and eventually was cancelled. By support of the well known geographer August Petermann (1822-1878) Weyprecht and Payer made a voyage into the Barents Sea which made them believe having seen the "open polar sea". An additional undertaking to confirm and to extend the find was obvious. At this stage of the affair count Hans Wilczek (1837-1922) got involved. He not only fostered a new expedition with a considerable sum of money, but he participated in commanding a support vessel to Novaya Zemlya. Wilczek managed to get home but the expedition vessel under Weyprecht's command became imprisoned in the pack for two years and at least had to be abandoned. After an adventurous trip back to civilisation Weyprecht changed his mind in what he considered the best way of polar research. Together with Wilczek in 1875 he started the promotion of international station-based polar exploration - the IPY was born. Wilczek guaranteed the constitution of an Austrian station on Novaya Zemlya and was ready to winter over there personally. Because of several political and other obstructions the beginning of the IPY was delayed till 1882. Wilczek's friend Weyprecht had passed away already. The command of the Austrian station, eventually erected on Jan Mayen, was given to Emil v. Wohlgemuth (1843-1896). Wilczek financed the main part of the Austrian IPY participation. Wilczek is described as honest and popular. On the one hand acquainted with the most prominent persons of his days, he respected everybody and had many relationships with scientists and artists. There is a kind of autobiography under the title: Hans Wilczek erzählt seinen Enkeln Erinnerungen aus seinem Leben (Hans Wilczek tells his grandchildren reminiscences from his life); edited by his daughter Elisabeth Kinsky-Wilczek, Graz 1933, 502 p. The book is available in an English version: Happy Retrospect - the Reminiscences of Count Wilczek 1837-1922, Bell and Sons, London 1934, 295 p.

(Table 6) Selenium isotopic composition of sediment samples from ODP Site 185-1149

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of other hydride-forming elements, such as Ge, Sb, and As. The analyte is introduced in the plasma torch with a continuous-flow hydride generation system. Instrumental mass fractionation is corrected with a "standard-sample bracketing" approach. By use of this new technique, the minimum Se required per analysis is lowered to 10 ng, which is one order of magnitude less than the amount needed for the N-TIMS technique. The estimated external precision calculated for the 82Se/76Se isotope ratio is 0.25? (2 sigma), and the data are reported as delta notation (?) relative to our internal standard (MERCK elemental standard solution). Measurements of Se isotopes are presented for samples of standard solutions and geological reference materials, such as silicate rocks, soils, and sediments. The Se isotopic composition of selected terrestrial and extraterrestrial materials are also presented. An overall Se isotope variation of 8? has been observed, suggesting that Se isotopes fractionate readily and are extremely useful tracers of natural processes.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.