(Table 2) Depth-age control points of ODP Site 177-1090

At Ocean Drilling Program (ODP) Site 1090 on the Agulhas Ridge (subantarctic South Atlantic) benthic foraminiferal stable isotope records span the late Oligocene through the early Miocene (25~16 Ma) at a temporal resolution of ?10 kyr. In the same time interval a magnetic polarity stratigraphy can be unequivocally correlated to the geomagnetic polarity timescale (GPTS), thereby providing secure correlation of the isotope record to the GPTS. On the basis of the isotope-magnetostratigraphic correlation we provide refined age calibration of established oxygen isotope events Mi1 through Mi2 as well as several other distinctive isotope events. Our data suggest that the d18O maximum commonly associated with the Oligocene/Miocene (O/M) boundary falls within C6Cn.2r (23.86 Ma). The d13C maximum coincides, within the temporal resolution of our record, with C6Cn.2n/r boundary and hence to the O/M boundary. Comparison of the stable isotope record from ODP Site 1090 to the orbitally tuned stable isotope record from ODP Site 929 across the O/M boundary shows that variability in the two records is very similar and can be correlated at and below the O/M boundary. Site 1090 stable isotope records also provide the first deep Southern Ocean end-member for reconstructions of circulation patterns and late Oligocene to early Miocene climate change. Comparison to previously published records suggests that basin to basin carbon isotope gradients were small or nonexistent and are inconclusive with respect to the direction of deep water flow. Oxygen isotope gradients between sites suggest that the deep Southern Ocean was cold in comparison to the North Atlantic, Indian, and the Pacific Oceans. Dominance of cold Southern Component Deep Water at Site 1090, at least until 17 Ma, suggests that relatively cold circumpolar climatic conditions prevailed during the late Oligocene and early Miocene. We believe that a relatively cold Southern Ocean reflects unrestricted circumpolar flow through the Drake Passage in agreement with bathymetric reconstructions.

Geochemistry of Eocene/Oligocene sediments of ODP Site 177-1090

The Agulhas Ridge, off the tip of Africa between the Atlantic and Indian Oceans, is ideally located to capture the evolution of Paleogene-early Neogene circulation patterns associated with global cooling. Multiproxy records of productivity (biogenic barium (Baex), opal, CaCO3 mass accumulation rates (MARs)), nutrient and organic carbon burial (reactive phosphorus (Pr) MARs), and redox state of deep waters (U enrichment) from Ocean Drilling Program (ODP) Site 1090 reflect hydrographic shifts in this region between the middle Eocene and early Oligocene (~9-33 Ma). Several peaks in increased export productivity and burial of organic matter occurred within the late Eocene (~36.5, ~34, and ~33.7 Ma), which along with surface hydrologic conditions favoring opaline organisms over calcareous organisms could have aided in the draw down of pCO2 to a threshold level that facilitated large ice sheet development on Antarctica in the earliest Oligocene. Our multiproxy approach illustrates the importance of vertical as well as spatial hydrographic reorganization in amplifying or driving climatic cooling of the middle Eocene to early Oligocene by facilitating increases in the relative or absolute burial of organic carbon.

Sea surface temperature estimates and alkenone C37:4 abundances in ODP Site 145-882 and 177-1090

The cold upwelling 'tongue' of the eastern equatorial Pacific is a central energetic feature of the ocean, dominating both the mean state and temporal variability of climate in the tropics and beyond. Recent evidence for the development of the modern cold tongue during the Pliocene-Pleistocene transition has been explained as the result of extratropical cooling that drove a shoaling of the thermocline. We have found that the sub-Antarctic and sub-Arctic regions underwent substantial cooling nearly synchronous to the cold tongue development, thereby providing support for this hypothesis. In addition, we show that sub-Antarctic climate changed in its response to Earth's orbital variations, from a subtropical to a subpolar pattern, as expected if cooling shrank the warm-water sphere of the ocean and thus contracted the subtropical gyres.

Nd and Sm isotopic record from fossil fish teeth recovered from ODP Site 177-1090

Neodymium (Nd) isotopes were measured on 181 samples of fossil fish teeth recovered from Oligocene to Miocene sections at Ocean Drilling Program Site 1090 (3700 m water depth) on Agulhas Ridge in the Atlantic sector of the Southern Ocean. A long-term decreasing trend toward less radiogenic Nd isotope compositions dominates the record. This trend is interrupted by shifts toward more radiogenic compositions near the early/late Oligocene boundary and the Oligocene/Miocene boundary. Overall, epsilon-Nd values at Agulhas Ridge are more radiogenic than at other Atlantic locations, and are similar to those at Indian Ocean locations. The pattern of variability is remarkably similar to Nd isotope results from Walvis Ridge (South Atlantic) and Ninetyeast Ridge (Indian Ocean). In contrast, Agulhas Ridge and Maud Rise Nd isotope records do not show similar patterns over this interval. Results from this study indicate that deep water in the Atlantic flowed predominantly from north to south during the Oligocene and Miocene, and that export of Northern Component Water (NCW) to the Southern Ocean increased in the late Oligocene. There is also evidence for efficient exchange of deep waters between the Atlantic sector of the Southern Ocean and the Indian Ocean, although the direction of deep water flow is not entirely clear from these data. The shifts to more radiogenic Nd isotopic compositions most likely represent increases in the flux of Pacific waters through Drake Passage, and the timing of these events reflect development of a mature Antarctic Circumpolar Current (ACC). The relative timing of increased NCW export and ACC maturation support hypotheses that link deep water formation in the North Atlantic to the opening of Drake Passage.

(Table T1) Iridium concentration in ODP Site 177-1090 sediments

Anomalous concentrations of Ir have been found in upper Eocene sediments from Ocean Drilling Program (ODP) Hole 1090B. Clear and dark-colored spherules that are believed to be microtektites and clinopyroxene-bearing microkrystites, respectively, were found in the samples with highest Ir. The peak Ir concentration in Sample 177-1090B-30X-5,105-106 (954 pg/g) and the net Ir fluence (14 ng/cm**2) at this site are higher than at most other localities except for Caribbean site RC9-58. The Ir anomaly and impact debris are probably correlative with similar deposits found at ODP Site 689 on the Maude Rise and at other localities around the world.

(Appendix A) Geochemistry of Oligocene sediments of ODP Site 177-1090

Ocean Drilling Program (ODP) Site 1090, on the Agulhas Ridge in the South Atlantic sector of the Southern Ocean, is ideally located to capture changes in Southern Ocean circulation patterns. Using samples taken from cored sediments, we construct multiproxy records of productivity (biogenic barium (Baex), opal, and CaCO3 mass accumulation rates (MARs)), nutrient and organic carbon burial (reactive phosphorus (Pr) MARs), and redox conditions (U and Mn enrichments) to investigate hydrographic conditions associated with climatic shifts from the Oligocene through the early Miocene. Orbitally induced cyclicity in U and Mn enrichments (100 kyr) suggests shifts in deepwater characteristics. However, CaCO3 dissolution coincident with low U and Mn enrichments does not indicate low-oxygen, corrosive waters similar to modern conditions. These observations indicate that a well-developed "modern-type" Antarctic Circumpolar Current (ACC) did not yet exist over the period from 30 to 20 Ma, with two potential consequences: The Southern Ocean was not functioning as a silica trap, permitting a broader distribution of silica that may have facilitated organic carbon burial in the ocean in general, and the lack of a deeply mixing ACC may have facilitated organic carbon burial in the Southern Ocean. Both the relative (high opal MARs coincident with low CaCO3 MARs) and absolute (high Pr MARs) burial of organic carbon suggest a powerful mechanism for pCO2 drawdown.

Plio-Pleistocene diatom biostratigraphy from ODP Leg 177, Atlantic sector of the Southern Ocean

Seven sites were drilled during Ocean Drilling Program Leg 177 in the Atlantic sector of the Southern Ocean (SO) on a transect over the Antarctic Circumpolar Current from the Subantarctic to the Antarctic Zone. At four sites sediments were recovered with a Pliocene/Pleistocene sediment package of up to 580 m allowing the refinement of previous diatom zonation concepts. Samples were analyzed on stratigraphic distribution and abundance of diatom species. A refined diatom biozonation tied to the geomagnetic polarity record is proposed. For the middle and late Pleistocene two zonations applicable to the northern and southern area of the SO were constructed, considering different latitudinal distributions of biostratigraphic diatom marker species. The southern zonation for the Pleistocene relies on the occurrence of species of the genus Rouxia, R. leventerae and R. constricta n. sp. as well as on a revised last occurrence datum (LOD) of Actinocyclus ingens (0.38 Ma, late marine isotope stage (MIS) 11). The use of these new stratigraphic marker species refines the temporal resolution for biostratigraphic age assignment to up to 0.1 Myr. In particular the LOD of R. leventerae as an indicator for the MIS 6/5 boundary (Termination II) will improve future dating of carbonate-free Antarctic sediments. These new data were obtained from sediments of Sites 1093 and 1094 (Antarctic Zone). The northern zonation for the middle and late Pleistocene time interval is based on the Pleistocene abundance pattern of Hemidiscus karstenii which was already proposed by previous investigations (e.g. Gersonde and Barcena, 1998). One new species (R. constricta) and two new combinations (Fragilariopsis clementia, Fragilariopsis reinholdii) are proposed in this study.

Relative abundance and ranges of selected diatoms from Pliocene-Pleistocene sections of ODP Leg 177, Atlantic sector of the Southern Ocean

During Ocean Drilling Program (ODP) Leg 177, seven sites were drilled aligned on a transect across the Antarctic Circumpolar Current in the Atlantic sector of the Southern Ocean. The primary scientific objective of Leg 177 was the study of the Cenozoic paleoceanographic and paleoclimatic history of the southern high latitudes and its relationship with the Antarctic cryosphere development. Of special emphasis was the recovery of Pliocene-Pleistocene sections, allowing paleoceanographic studies at millennial or higher time resolution, and the establishment of refined biostratigraphic zonations tied to the geomagnetic polarity record and stable isotope records. At most sites, multiple holes were drilled to ensure complete recovery of the section. A description of the recovered sections and the construction of a multihole splice for the establishment of a continuous composite is presented in the Leg 177 Initial Reports volume for each of the sites (Gersonde, Hodell, Blum, et al., 1999). Here we present the relative abundance pattern and the stratigraphic ranges of diatom taxa encountered from shore-based light microscope studies completed on the Pliocene-Pleistocene sequences from six of the drilled sites (Sites 1089-1094). No shore-based diatom studies have been conducted on the Pliocene-Pleistocene sediments obtained at Site 1088, located on the northern crest of the Agulhas Ridge, because of the scattered occurrence and poor preservation of diatoms in these sections (Shipboard Scientific Party, 1999b). The data included in our report present the baseline of a diatom biostratigraphic study of Zielinski and Gersonde (2002), which (1) includes a refinement of the southern high-latitude Pliocene-Pleistocene diatom zonation, in particular for the middle and late Pleistocene, and (2) presents a biostratigraphic framework for the establishment of age models of the recovered sediment sections. Zielinski and Gersonde (2002) correlated the diatom ranges with the geomagnetic polarity record established shipboard (Sites 1090 and 1092) (Shipboard Scientific Party, 1999c, 1999d) and on shore (Sites 1089, 1091, 1093, and 1094) by Channell and Stoner (2002). The Pliocene-Pleistocene diatom zonation proposed by Zielinski and Gersonde (2002) relies on a diatom zonation from Gersonde and Bárcena (1998) for the northern belt of the Southern Ocean. Because of latitudinal differentiation of sea-surface temperature, nutrients, and salinity between Antarctic and Subantarctic/subtropical water masses, the Pliocene-Pleistocene stratigraphic marker diatoms are not uniformly distributed in the Southern Ocean (Fenner, 1991; Gersonde and Bárcena, 1998). As a consequence, Zielinski and Gersonde (2002) propose two diatom zonations for application in the Antarctic Zone south of the Polar Front (Southern Zonation, Sites 1094 and 1093) and the area encompassing the Polar Front Zone (PFZ) and the Subantarctic Zone (Northern Zonation, Sites 1089-1092). This accounts especially for the Pleistocene zonation where Hemidiscus karstenii, whose first abundant occurrence datum and last occurrence datum defines the subzonation of the northern Thalassiosira lentiginosa Zone, occurs only sporadically in the cold-water realm south of the PFZ and thus is not applicable in sections from this area. However, newly established marker species assigned to the genus Rouxia (Rouxia leventerae and Rouxia constricta) are more related to cold-water environments and allow a refinement of the Pleistocene stratigraphic zonation for the southern cold areas. A study relying on quantitative counts of both Rouxia species confirms the utility of these stratigraphic markers for the identification of sequences attributed to marine isotope Stages 6 and 8 in the southern Southern Ocean (Zielinski et al., 2002).