Element abundances, loss on ignition, total analyzed abundances, CIA values, and Al-oxide/Ti-oxide ratios of sediment core CRP-2A (Table1)

The CRP-2/2A core, drilled in western McMurdo Sound in October and November 1998, penetrated 624 m of Quaternary. Pliocene, lower Miocene, and Oligocene glacigenic sediments. The palaeoclimatic record of CRP-2/2A is examined using major element analyses of bulk core samples of fine grained sediments (mudstones and siltstones) and the Chemical Index of Alteration (CIA) of Nesbitt & Young (1982). The CIA is calculated from the relative abundances of AI, K, Ca, and Na oxides, and its magnitude increases as the effects of chemical weathering increase. However, changes in sediment provenance can also affect the CIA, and provenance changes are recorded by shifts in the Al2O3/TiO2 ratios and the Nb contents of these CRP-2/2A mudstones. Relatively low CIA values (40-50) occur throughout the CRP-2/2A sequence, whereas the Al2O3/TiO2 ratio decreases upsection. The major provenance change is an abrupt onset of McMurdo Volcanic Group detritus at ~300 mbsf and is best characterized by a rapid increase in Nb content in the sediments. This provenance shift is not evident in the CIA record, suggesting that a contribution from the Ferrar Dolerite to the older sediments was replaced by an input of McMurdo Volcanic Group material in the younger sediments. If this is true, then the relatively uniform CIA values indicate relatively consistent palaeoweathering intensities throughout the Oligocene and early Miocene in the areas that supplied sediment to CRP-2/2A.

(Appendix) Stable carbon and oxygen isotopes, and Mg/Ca ratios of foraminifera from ODP Hole 154-925A

To better understand the links between the carbon cycle and changes in past climate over tectonic timescales we need new geochemical proxy records of secular change in silicate weathering rates. A number of proxies are under development, but some of the most promising (e.g. palaeoseawater records of Li and Nd isotope change) can only be employed on such large samples of mono-specific foraminifera that application to the deep sea sediment core archive becomes highly problematic. "Dentoglobigerina" venezuelana presents a potentially attractive target for circumventing this problem because it is a typically large (> 355 ?m diameter), abundant and cosmopolitan planktic foraminifer that ranges from the early Oligocene to early Pliocene. Yet considerable taxonomic and ecological uncertainties associated with this taxon must first be addressed. Here, we assess the taxonomy, palaeoecology, and ontogeny of "D." venezuelana using stable isotope (oxygen and carbon) and Mg/Ca data measured in tests of late Oligocene to early Miocene age from Ocean Drilling Program (ODP) Site 925, on Ceara Rise, in the western equatorial Atlantic. To help constrain the depth habitat of "D." venezuelana relative to other species we report the stable isotope composition of selected planktic foraminifera species within Globigerina, Globigerinoides, Paragloborotalia and Catapsydrax. We define three morphotypes of "D." venezuelana based on the morphology of the final chamber and aperture architecture. We determine the trace element and stable isotope composition of each morphotype for different size fractions, to test the validity of pooling these morphotypes for the purposes of generating geochemical proxy datasets and to assess any ontogenetic variations in depth habitat. Our data indicate that "D." venezuelana maintains a lower thermocline depth habitat at Ceara Rise between 24 and 21 Ma. Comparing our results to published datasets we conclude that this lower thermocline depth ecology for the Oligo-Miocene is part of an Eocene-to-Pliocene evolution of depth habitat from surface to sub-thermocline for "D." venezuelana. Our size fraction data advocate the absence of photosymbionts in "D." venezuelana and suggest that juveniles calcify higher in the water column, descending into slightly deeper water during the later stages of its life cycle. Our morphotype data show that d18O and d13C variation between morphotypes is no greater than within-morphotype variability. This finding will permit future pooling of morphotypes in the generation of the "sample hungry" palaeoceanographic records.

Color reflectance and XRF drill core scanner data of ANDRILL core AND-2A

The compositional record of the AND-2A drillcore is examined using petrological, sedimentological, volcanological and geochemical analysis of clasts, sediments and pore waters. Preliminary investigations of basement clasts (granitoids and metasediments) indicate both local and distal sources corresponding to variable ice-volume and ice-flow directions. Low abundance of sedimentary clasts (e.g., arkose, litharenite) suggests reduced contributions from sedimentary covers while intraclasts (e.g., diamictite, conglomerate) attest to intrabasinal reworking. Volcanic material includes pyroclasts (e.g., pumice, scoria), sediments and lava. Primary and reworked tephra layers occur within the Early Miocene interval (1093 to 640 metres below sea floor mbsf). The compositions of volcanic clasts reveal a diversity of alkaline types derived from the McMurdo Volcanic Group. Finer-grained sediments (e.g., sandstone, siltstone) show increases in biogenic silica and volcanic glass from 230 to 780 mbsf and higher proportions of terrigenous material c. 350 to 750 mbsf and below 970 mbsf. Basement clast assemblages suggest a dominant provenance from the Skelton Glacier - Darwin Glacier area and from the Ferrar Glacier - Koettlitz Glacier area. Provenance of sand grains is consistent with clast sources. Thirteen Geochemical Units are established based on compositional trends derived from continuous XRF scanning. High values of Fe and Ti indicate terrigenous and volcanic sources, whereas high Ca values signify either biogenic or diagenic sources. Highly alkaline and saline pore waters were produced by chemical exchange with glass at moderately elevated temperatures.

Seafloor spreading magnetic anomaly isochron map compilation for the Weddell Sea and Scotia Sea

The deep sea sedimentary record is an archive of the pre-glacial to glacial development of Antarctica and changes in climate, tectonics and ocean circulation. Identification of the pre-glacial, transitional and full glacial components in the sedimentary record is necessary for ice sheet reconstruction and to build circum-Antarctic sediment thickness grids for past topography and bathymetry reconstructions, which constrain paleoclimate models. A ~3300 km long Weddell Sea to Scotia Sea transect consisting of multichannel seismic reflection data from various organisations, were used to interpret new horizons to define the initial basin-wide seismostratigraphy and to identify the pre-glacial to glacial components. We mapped seven main units of which three are in the inferred Cretaceous-Paleocene pre-glacial regime, one in the Eocene-Oligocene transitional regime and three units in the Miocene-Pleistocene full glacial climate regime. Sparse borehole data from ODP leg 113 and SHALDRIL constrain the ages of the upper three units. Compiled seafloor spreading magnetic anomalies constrain the basement ages and the hypothetical age model. In many cases, the new horizons and stratigraphy contradict the interpretations in local studies. Each seismic sedimentary unit and its associated base horizon are continuous and traceable for the entire transect length, but reflect a lateral change in age whilst representing the same deposition process. The up to 1240 m thick pre-glacial seismic units form a mound in the central Weddell Sea basin and, in conjunction with the eroded flank geometry, support the interpretation of a Cretaceous proto-Weddell Gyre. The base reflector of the transitional seismic unit, which marks the initial ice sheet advances to the outer shelf, has a lateral model age of 26.6-15.5 Ma from southeast to northwest. The Pliocene-Pleistocene glacial deposits reveals lower sedimentations rates, indicating a reduced sediment supply. Sedimentation rates for the pre-glacial, transitional and full glacial components are highest around the Antarctic Peninsula, indicating higher erosion and sediment supply of a younger basement. We interpret an Eocene East Antarctic Ice Sheet expansion, Oligocene grounding of the West Antarctic Ice Sheet and Early Miocene grounding of the Antarctic Peninsula Ice Sheet.

(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.

Late Miocene-early Pliocene stable isotope record of benthic foraminifera from ODP Site 177-1088 in the sub-Antarctic South Atlantic

Benthic foraminiferal stable isotope records for the past 11 Myr from a recently drilled site in the sub-Antarctic South Atlantic (Site 1088, Ocean Drilling Program Leg 177, 41°S, 15°E, 2082 m water depth) provide, for the first time, a continuous long-term perspective on deep water distribution patterns and Southern Ocean climate change from the late Miocene through the early Pliocene. I have compiled published late Miocene through Pliocene stable isotope records to place the new South Atlantic record in a global framework. Carbon isotope gradients between the North Atlantic, South Atlantic, and Pacific indicate that a nutrient-depleted watermass, probably of North Atlantic origin, reached the sub-Antarctic South Atlantic after 6.6 Ma. By 6.0 Ma the relative proportion of the northern-provenance watermass was similar to today and by the early Pliocene it had increased to greater than the modern proportion suggesting that thermohaline overturn in the Atlantic was relatively strong prior to the early Pliocene interval of inferred climatic warmth. Site 1088 oxygen isotope values display a two-step increase between ~7.4 Ma and 6.9 Ma, a trend that parallels a published delta18O record of a site on the Atlantic coast of Morocco. This is perhaps best explained by a gradual cooling of watermasses that were sinking in the Southern Ocean. I speculate that relatively strong thermohaline overturn at rates comparable to the present day interglacial interval during the latest Miocene may have provided the initial conditions for early Pliocene climatic warmth. The impact of an emerging Central American Seaway on Atlantic-Pacific Ocean upper water exchange may have been felt in the North Atlantic beginning in the latest Miocene between 6.6 and 6.0 Ma, which would be ~1.5 Myr earlier than previously thought.

Geochemistry, sediment components, and paleoproductivity reconstruction for the Miocene to early Pliocene sediments

We reconstruct paleoproductivity at three sites in the Atlantic Ocean (Ocean Drilling Program Sites 982, 925, and 1088) to investigate the presence and extent of the late Miocene to early Pliocene 'biogenic bloom' from 9 to 3 Ma. Our approach involves construction of multiple records including benthic foraminiferal and CaCO3 accumulation rates, Uvigerina counts, dissolution proxies, and geochemical tracers for biogenic and detrital fluxes. This time interval also contains the so-called late Miocene carbon isotope shift, a well-known decrease in benthic foraminiferal d13C values. We find that the timing of paleoproductivity maxima differs among the three sites. At Site 982 (North Atlantic), benthic foraminifera and CaCO3 accumulation were both at a maximum at ~5 Ma, with smaller peaks at ~6 Ma. The paleoproductivity maximum was centered earlier (~6.6-6.0 Ma) in the tropical Atlantic (Site 925). In the South Atlantic (Site 1088), paleoproductivity increased even earlier, between 8.2 Ma and 6.2 Ma, and remained relatively high until ~5.4 Ma. We note that there is some overlap between the interval of maximum productivity between Sites 925 and 1088, as well as the minor productivity increase at Site 982. We conclude that the paleoproductivity results support hypotheses aiming to place the biogenic bloom into a global context of enhanced productivity. In addition, we find that at all three sites the d13C shift is accompanied by carbonate dissolution. This observation is consistent with published studies that have sought a relationship between the late Miocene carbon isotope shift and carbonate preservation.

Early to middle Miocene radiolarian stratigraphy of the Kerguelen Plateau, Southern Ocean

Early to middle Miocene radiolarian assemblages were examined at three sites (747, 748, and 751) that were cored during Ocean Drilling Program Leg 120 south of the present polar frontal zone on the Kerguelen Plateau (Indian sector of the Southern Ocean). The radiolarian biostratigraphic study relies on a radiolarian zonation recently developed on Leg 113 materials in the Atlantic sector of the Southern Ocean, which is correlated with the geomagnetic time scale. New radiolarian biostratigraphic data also considering the established geomagnetic polarity record were used to improve and emend the age calibration of some lower Miocene radiolarian zones and a redefined middle Miocene radiolarian zonation is proposed. Based on these results, a revised age assignment of the lower Miocene sections drilled at Leg 113 Sites 689 and 690 is proposed.

Latest Oligocene through early middle Miocene diatom biostratigraphy of the eastern tropical Pacific

Study of DSDP Sites 71, 77, and 495 has allowed the development of a refined diatom biostratigraphy for the latest Oligocene through early middle Miocene of the eastern tropical Pacific which is well correlated to the low-latitude zonations for planktonic foraminifers, coccoliths, and radiolarians. Six zones and 7 subzones are proposed, and correlation with high-latitude diatoms zonations for the North Pacific, the Norwegian Sea, and the Southern Ocean is suggested by the discovery of selected diatoms in these tropical sediments which were previously thought to be restricted to high latitudes. Six new species and one new variety of diatoms which are stratigraphically useful are proposed : Actinocyclus hajosiae, n. sp., A. radionovae, n. sp., Coscinodiscus blysmos, n. sp., C. praenodulifer, n. sp., Craspedodiscus rydei, n. sp., Thalassiosira bukryi, n. sp., and Coscinodiscus lewisianus var. robustus n. var.

Stable carbon and oxygen isotope ratios of Late Miocene and Early Pliocene foraminifera from the Southwest Pacific

The Late Miocene-Early Pliocene paleoclimatic history has been evaluated for a deep drilled sediment sequence at Deep Sea Drilling Project Site 281 and a shallow water marine sediment sequence at Blind River, New Zealand, both of which lay within the Subantarctic water mass during the Late Miocene. A major, faunally determined, cooling event within the latest Miocene at Site 281 and Blind River coincides with oxygen isotopic changes in benthonic foraminiferal composition at DSDP Site 284 considered by Shackleton and Kennett (1975) to indicate a significant increase in Antarctic ice sheet volume. However, at Site 281 benthonic foraminiferal oxygen isotopic changes do not record such a large increase in Antarctic ice volume. It is possible that the critical interval is within an unsampled section (no recovery) in the latest Miocene. Two benthonic oxygen isotopic events in the Late Miocene (0.5 ? and 1 ? in the light direction) may be useful as time-stratigraphic markers. A permanent, negative, carbon isotopic shift at both Site 281 and Blind River allows precise correlations to be made between the two sections and to other sites in the Pacific region. Close interval sampling below the carbon shift at Site 281 revealed dramatic fluctuations in surface-water temperatures prior to a latest Miocene interval of refrigeration (Kapitean) and a strong pulse of dissolution between 6.6 and 6.2 +/- 0.1 m.y. which may be related to a fundamental geochemical change in the oceans at the time of the carbon shift (6.3-6.2 m.y.). No similar close interval sampling at Blind River was possible because of a lack of outcrop over the critical interval. Paleoclimatic histories from the two sections are very similar. Surface water temperatures and Antarctic ice-cap volume appear to have been relatively stable during the late Middle-early Late Miocene (early-late Tongaporutuan). By 6.4 m.y. cooler conditions prevailed at Site 281. Between 6.3 and 6.2 -+ 0.1 m.y. the carbon isotopic shift occurred followed, within 100,000 yr, by a distinct shallowing of water depths at Blind River. The earliest Pliocene (Opoitian) is marked by increasing surface-water temperatures.

Late Miocene to Early Pliocene radiolarians from ODP Hole 178-1095B

Early Pliocene to middle late Miocene hemipelagic and distal turbidite sediments from Hole 1095B, near the Antarctic Peninsula, yield moderately abundant, moderately well preserved radiolarian faunas and other biosiliceous material (diatoms, silicoflagellates, and sponge spicules). Preservation characteristics, however, vary strongly even between closely related samples, and there are many intervals of poor preservation. In the 140- to 460-meters below seafloor interval studied, it was possible to identify the following standard Southern Ocean radiolarian zones: Upsilon, Tau, Amphymenium challengerae, Acrosphaera? labrata, Siphonosphaera vesuvius, and upper Acrosphaera australis (total age range ~4-10 Ma). Some normally common radiolarian groups, such as actinommids, are unusually rare in the studied material, and the relative ranges of several individual species, such as Acrosphaera labrata vs. A. australis, appear to be somewhat anomalous. These observations imply that the ranges of taxa in this section may be somewhat diachronous, due to either local ecologic factors and/or the highly variable preservation of the faunas. Thus, the ages of events reported are probably only approximate, although they are still useful for constraining the age of sediments in this section.

Sedimentation rates and geochemistry of the Atlantic and Indic Ocean of Late Miocene - Early Pliocene

Studies of the late Miocene-early Pliocene biogenic bloom typically have focused on high-productivity areas in the Indian and Pacific Oceans in order to achieve high resolution samples. Thus there is a paucity of information concerning whether the Atlantic Ocean, in general or low-productivity regions in all three basins experienced this bloom. This study measured the phosphorus mass accumulation rate (PMAR). in five cores from low-productivity regions of the Atlantic and Indian Oceans. All cores exhibit a peak in productivity 4-5.5 Ma, coincident with the Indo-Pacific bloom. This suggests that nutrients were not shifted away from low-productivity regions nor out of the Atlantic Ocean. Instead, it appears that the bloom was caused by an overall increase in nutrient flux into the world oceans. Four of the cores record the bloom's PMAR peak as bimodal, indicating a pulsed increase in phosphorus to the oceans. This suggests that there may have been multiple causes of the biogenic bloom.