Biostratigraphic significance of the calcareous nannofossil genus Reticulofenestra in the Upper Pliocene of the North Atlantic

We demonstrate size fluctuations of the calcareous nannofossil genus Reticulofenestra in Upper Pliocene sediments from the North Atlantic Ocean and clarify a characteristic evolutionary trend of this genus. Four bioevents, which are based on abrupt decreases in maximum size and on changes of morphologic features of Reticulofenestra specimens, are detected in the sediments. They are the disappearance of R. minutula var. A, the termination of Acme Zone II of R. minutula var. C, the disappearance of R. minutula var. B, and the termination of Acme Zone I of R. minutula var. C, in ascending order. These are nearly synchronous and traceable events.

The occurrence and significance of Pleistocene and Upper Pliocene sapropels

Numerous sapropels and sapropelic strata from Upper Pliocene and Pleistocene hemipelagic sediments of the Tyrrhenian Sea show that intermittent anoxia, possibly related to strongly increased biological productivity, was not restricted to the eastern Mediterranean basins and may be a basin-wide result of Late Pliocene-Pleistocene climatic variability. Even though the sapropel assemblage of the Tyrrhenian Sea clearly originates from multiple processes such as deposition under anoxic conditions or during spikes in surface water productivity and lateral transport of organic-rich suspensates, many "pelagic sapropels" have been recognized. Stratigraphic ages calculated for the organic-rich strata recovered during ODP Leg 107 indicate that the frequency of sapropel formation increased from the lowermost Pleistocene to the base of the Jaramillo magnetic event, coinciding with a period when stable isotope records of planktonic foraminifera indicate the onset of climatic cooling in the Mediterranean. A second, very pronounced peak in sapropel formation occurred in the Middle to Late Pleistocene (0.73-0.26 Ma). Formainifers studied in three high-resolution sample sets suggest that changes in surface-water temperature may have been responsible for establishing anoxic conditions, while salinity differences were not noted in the faunal assemblage. However, comparison of sapropel occurrence at Site 653 with the oxygen isotopic record of planktonic foraminifers established by Thunell et al. (1990, doi:10.2973/odp.proc.sr.107.155.1990) indicates that sapropel occurrences coincide with negative d18O excursions in planktonic foraminifers in thirteen of eighteen sapropels recognized in Hole 653A. A variant of the meltwater hypothesis accepted for sapropel formation in the Late Pleistocene eastern Mediterranean may thus be the cause of several "anoxic events" in the Tyrrhenian as well. Model calculations indicate that the amount of oxygen advection from Western Mediterranean Deep Water exerts the dominant control on the oxygen content in deep water of the Tyrrhenian Sea. Inhibition of deep-water formation in the northern Adriatic and the Balearic Basin by increased meltwater discharge and changing storm patterns during climatic amelioration may thus be responsible for sapropel formation in the Tyrrhenian Sea.

Stable isotope ratios and abundances of selected foraminifera taxa from ODP Leg 172 sites

This data report describes the results of post-Leg 172 sampling of Sites 1054, 1055, and 1063 for two purposes: to investigate the climatic significance of red-colored intervals in the hemipelagic sediments cored during Leg 172 and to better understand the stratigraphy and chronology of Carolina Slope Sites 1054 and 1055. Gravity cores collected from the Carolina Slope on site survey cruise Knorr 140/2 show very high rates of sedimentation during the Holocene and lower rates during the last glacial maximum (LGM). Because of the high rates, many of the sediments in the recovered cores never reached the LGM. In other cores, it is possible that deglacial oscillations have been mistaken for the LGM. Although radiocarbon dating could solve that problem, some of the gravity cores are at or very close to the Ocean Drilling Program (ODP) sites, and it is useful to compare the isotope stratigraphies among them before proceeding with dating. Furthermore, some of the site survey cores have red-colored intervals and others do not, even though there is some indication they are time equivalent. Either the stratigraphy is wrong, diagenesis has affected the color of the sediment, or red sediment is carried to some sites but not to others that differ in depth by only a few hundred meters.

Mg/Ca ratios of Cenozoic benthic foraminifera from the Indian and South Atlantic Ocean

We investigate the evolution of Cenozoic climate and ice volume as evidenced by the oxygen isotopic composition of seawater (delta18Osw) derived from benthic foraminiferal Mg/Ca ratios to constrain the temperature effect contained in foraminiferal delta18O values. We have constructed two benthic foraminiferal Mg/Ca records from intermediate water depth sites (Ocean Drilling Program sites 757 and 689 from the subtropical Indian Ocean and the Weddell Sea, respectively). Together with the previously published composite record of Lear et al. (2002, doi:10.1126/science.287.5451.269) and the Neogene record from the Southern Ocean of Billups and Schrag (2002, doi:10.1029/2000PA000567), we obtain three, almost complete representations of the delta18Osw for the past 52 Myr. We discuss the sensitivity of early Cenozoic Mg/Ca-derived paleotemperatures (and hence the delta18Osw) to assumptions about seawater Mg/Ca ratios. We find that during the middle Eocene (~ 49-40 Ma), modern seawater ratios yield Mg/Ca-derived temperatures that are in good agreement with the oxygen isotope paleothermometer assuming ice-free conditions. Intermediate waters cooled during the middle Eocene reaching minimum temperatures by 40 Ma. The corresponding delta18Osw reconstructions support ice growth on Antarctica beginning by at least 40 Ma. At the Eocene/Oligocene boundary, Mg/Ca ratios (and hence temperatures) from Weddell Sea site 689 display a well-defined maximum. We caution against a paleoclimatic significance of this result and put forth that the partitioning coefficient of Mg in benthic foraminifera may be sensitive to factors other than temperature. Throughout the remainder of the Cenozoic, the temporal variability among delta18Osw records is similar and similar to longer-term trends in the benthic foraminiferal delta18O record. An exception occurs during the Pliocene when delta18Osw minima in two of the three records suggest reductions in global ice volume that are not apparent in foraminiferal delta18O records, which provides a new perspective to the ongoing debate about the stability of the Antarctic ice sheet. Maximum delta18Osw values recorded during the Pleistocene at Southern Ocean site 747 agree well with values derived from the geochemistry of pore waters (Schrag et al., 1996, doi:10.1126/science.272.5270.1930) further highlighting the value of the new Mg/Ca calibrations of Martin et al. (2002, doi:10.1016/S0012-821X(02)00472-7) and Lear et al. (2002, doi:10.1016/S0016-7037(02)00941-9) applied in this study. We conclude that the application of foraminiferal Mg/Ca ratios allows a refined view of Cenozoic ice volume history despite uncertainties related to the geochemical cycling of Mg and Ca on long time scales.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

(Table 2) Age determination of sediment cores MD95-2002 and MD03-2692

We have compiled results obtained from four high sedimentation rate hemipelagic sequences from the Celtic sector of the NW European margin (NE Atlantic) to investigate the paleoceanographic and paleoclimatic evolution of the area over the last few climatic cycles. We focus on periods characteristic of deglacial transitions. We adopt a multiproxy sedimentological, geochemical, and micropaleontological approach, applying a sampling resolution down to ten microns for specific intervals. The investigation demonstrates the relationships between the Bay of Biscay hydrography and the glacial/deglacial history of both the proximal British-Irish Ice Sheet (BIIS) and the western European continent. We identify recurrent phases of laminae deposition concurrent with major BIIS deglacial episodes in all the studied cores. Evidence for abrupt freshwater discharges into the open ocean highlights the influence of such events at a regional scale. We discuss their impact at a global scale considering the present and past key location of the Bay of Biscay versus the Atlantic Meridional Overturning Circulation (AMOC).