Appendix A Table SD1. CaCO3, d18O, d13C and Sr isotopes from ODP Site 181-1120

An integrated chemostratigraphic (87Sr/86Sr, d13C and 18O) study of benthic foraminifera is presented for a 210 m-thick, intermediate depth (upper/middle bathyal transition), Miocene nannofossil ooze section of Ocean Drilling Program Site 1120, Campbell Plateau off New Zealand. Our results indicate that new 87Sr/86Sr, d13C and d18O profiles are wholly consistent with their respective Miocene reference curves. These observations facilitate identification of a total of five reliable chemostratigraphic datums, which are based on the fundamental structural changes in the 87Sr/86Sr curve and paired simultaneous d13C and d18O events. The resultant age-depth relationship clearly shows that the Miocene (20-5 Ma) biopelagic sedimentation on the Campbell Plateau was essentially continuous at a moderate to high, linear sedimentation rate (17.5 m/m.y. with an exception of the uppermost 13 m). Our findings do not support the shipboard biostratigraphic age model, which assumes that the critical early-middle Miocene transition was interrupted by a major hiatus (<~3 m.y.). Because of its unique bathymetric setting at a paleowater-depth of ~ 600 m, which is among the shallowest of the coeval isotopically studied deep-sea sections in the South Pacific/Southern Ocean, Site 1120 will serve as a reference section for surveying the evolution of intermediate-water paleoceanography in the Southern Hemisphere across the middle Miocene climatic transition.

Uvigerina spp. d18O and Mg/Ca measurements from sediment cores JR244-GC528 and MD07-3076

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected d18O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer d13C and foraminifer/coral 14C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.

(Table 1) Oxygen and carbon isotope ratios of benthic foraminifera of DSDP Holes 12-119 and 48-401

We present here oxygen and carbon isotopic records of Eocene to Oligocene benthic foraminifera from two Bay of Biscay Deep Sea Drilling Project (DSDP) sites (119 and 401). d18O of benthic foraminifera increases 1.9 per mil from a middle Eocene minimum (Zones P10-P11) to an earliest Oligocene maximum (Zone NP21). Approximately 1.4 per mil of the increase in benthic foraminiferal d18O occurs during the late Eocene to earliest Oligocene (Zones P15/16-NP21). Previous results from other North Atlantic DSDP sites (400A and 398) have significantly lower d18O values of benthic foraminifera, some by as much as 2 per mil (Vergnaud-Grazzini et al., 1978; 1989, doi:10.2973/dsdp.proc.48.119.1979; Vergnaud-Grazzini, 1979, doi:10.2973/dsdp.proc.47-2.117.1979 ). We believe that these differences result from diagenetic alteration of the sediments in the deeper-buried Sites 400A and 398.

Stable isotope record of benthic and planktonic foraminifera in sediment cores of ODP Leg 177, Southern Ocean

While onboard ship during Leg 177, we used variations in sediment physical properties (mainly percent color reflectance) in conjunction with biomagnetostratigraphy to correlate among sites and predict the position of marine isotope stages (MISs) (e.g., see fig. F11 in Shipboard Scientific Party, 1999, p. 45). Our working assumption was that physical properties of Leg 177 sediments are controlled mainly by variations in carbonate content. Previous studies of Southern Ocean sediment cores have shown that carbonate concentrations are relatively high during interglacial stages and low during glacial stages at sites located within the Polar Frontal Zone (PFZ). Today, the PFZ marks a lithologic boundary in underlying sediment separating calcareous oozes to the north and silica-rich facies to the south (Hays et al., 1976). Although there is debate whether the position of the "physical" PFZ actually moved during glacial-interglacial cycles (Charles and Fairbanks, 1990; Matsumoto et al., 2001), the "biochemical" PFZ, as expressed by the CaCO3/opal boundary in sediments, certainly migrated north during glacials and south during interglacials. This gave rise to lithologic variations that are useful for stratigraphic correlation. At Leg 177 sites located north of the PFZ and at sublysoclinal depths, we expected the same pattern of carbonate variation because cores in the Atlantic basin are marked by increased carbonate dissolution during glacial periods and increased preservation during interglacials (Crowley, 1985).

Sedimentology and stable oxygen isotope ratios of foraminifera from cores of the Porcupine Seabight, Northeast Atlantic

Large carbonate mound structures have been discovered in the northern Porcupine Seabight (Northeast Atlantic) at depths between 600 and 1000 m. These mounds are associated with the growth of deep-sea corals Lophelia pertusa and Madrepra oculata. In this study, three sediment cores have been analysed. They are from locations close to Propeller Mound, a 150 m high ridge-like feature covered with a cold-water coral ecosystem at its upper flanks. The investigations are concentrated on grain-size analyses, carbon measurements and on the visual description of the cores and computer tomographic images, to evaluate sediment content and structure. The cores portray the depositional history of the past ~31 kyr BP, mainly controlled by sea-level fluctuations and the climate regime with the advance and retreat of the Irish Ice Sheet onto the Irish Mainland Shelf. A first advance of glaciers is indicated by a turbiditic release slightly older than 31 kyr BP, coherent with Heinrich event 3 deposition. During Late Marine Isotope Stage 3 (MIS 3) and MIS 2 shelf erosion prevailed with abundant gravity flows and turbidity currents. A change from glaciomarine to hemipelagic contourite sedimentation during the onset of the Holocene indicates the establishment of the strong, present-day hydrodynamic regime at intermediate depths. The general decrease in accumulation of sediments with decreasing distance towards Propeller Mound suggests that currents (turbidity currents, gravity flows, bottom currents) had a generally stronger impact on the sediment accumulation at the mound base for the past ~31 kyr BP, respectively.

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.

Stable oxygen and carbon isotope ratios of Pliocene benthic foraminifera in the Atlantic Ocean

Large changes in benthic foraminiferal delta180 and delta13C occurred during the Pliocene (between 3.0 and 2.0 Ma) at Hole 665A. Oxygen isotopic compositions increased to maximum values at 2.4 Ma, correlating with an 18O enrichment observed at Hole 552A and other locations (Shackleton et al., 1984). As at Hole 606 (Keigwin, 1986), however, maximum delta180 values at 2.4 Ma were not as great as at Hole 552A, and enrichments in delta180 also occurred before 2.4 Ma. We believe that the section representing sediments from 2.5 to 2.7 or 2.8 Ma is missing at Hole 552A because of incomplete core recovery. Consequently, the older delta180 increases are not found at Hole 552A. Benthic foraminiferal delta13C values are much lower at Hole 665A than at Hole 552A, approaching the low values observed in the Pliocene Pacific Ocean. This geographic distribution of delta13C suggests that, like late Quaternary glaciations, the equatorial Atlantic Ocean was dominated during the Pliocene by deep water that originated in the Southern Ocean and had chemical characteristics very similar to the Pacific Ocean. Reduced O2 values were probably associated with low delta13C values and contributed to increased preservation of organic carbon during enriched 180 intervals of the Pliocene equatorial Atlantic.

Stable isotope record, Mg/Ca ratios and age model of St. Stephens Quarry, Alabama

In the largest global cooling event of the Cenozoic Era, between 33.8 and 33.5 Myr ago, warm, high-CO2 conditions gave way to the variable 'icehouse' climates that prevail today. Despite intense study, the history of cooling versus ice-sheet growth and sea-level fall reconstructed from oxygen isotope values in marine sediments at the transition has not been resolved. Here, we analyse oxygen isotopes and Mg/Ca ratios of benthic foraminifera, and integrate the results with the stratigraphic record of sea-level change across the Eocene-Oligocene transition from a continental-shelf site at Saint Stephens Quarry, Alabama. Comparisons with deep-sea (Sites 522 (South Atlantic) and 1218 (Pacific)) d18O and Mg/Ca records enable us to reconstruct temperature, ice-volume and sea-level changes across the climate transition. Our records show that the transition occurred in at least three distinct steps, with an increasing influence of ice volume on the oxygen isotope record as the transition progressed. By the early Oligocene, ice sheets were ~25% larger than present. This growth was associated with a relative sea-level decrease of approximately 105 m, which equates to a 67 m eustatic fall.

Stable carbon and oxygen isotope ratios of foraminifera in surface sediments of the South China Sea

The relationship between planktonic and benthic foraminiferal stable-isotope values and oceanographic conditions and factors controlling isotopic variations are discussed on the basis of oxygen and carbon isotopic analyses of 192 modern surface and Last Glacial Maximum (LGM) samples from the South China Sea (SCS). The harmonic variation of benthic delta18O in surface sediments with water depth and temperature implies that the temperature is the main factor influencing benthic delta18O variations. Planktonic delta18O fluctuates with sea surface temperature (SST) and salinity (SSS). The N-S temperature gradient results in planktonic delta18O decreasing from the northeast to the south. Cool, saline waters driven by the winter monsoon are interpreted to have been responsible for the high delta18O values in the northeast SCS. The East Asian monsoons not only bring nutrients into the South China Sea and maintain high nutrient concentration levels at the southwestern and northeastern ends, which cause depleted delta13C both in planktonic (surface) and benthic (bottom) samples but also reduce planktonic/benthic delta18O differences. The distribution of delta18O and delta13C in the surface and LGM samples are strikingly similar, indicating that the impact of SST and SSS has been maintained, and nutrient inputs, mainly from the northeastern and southwestern ends, have been controlled by monsoons since the LGM. Comparisons of the modern and LGM delta18O indicate a difference of about 3.6 °C in bottom-water temperature and a large surface-to-bottom temperature gradient during the LGM as compared to today.

Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

Stable oxygen isotope record of epibenthic foraminifera and water samples of the Arctic Ocean

We determined d18OCib values of live (Rose Bengal stained) and dead epibenthic foraminifera Cibicidoides wuellerstorfi, Cibicides lobatulus, and Cibicides refulgens in surface sediment samples from the Arctic Ocean and the Greenland, Iceland, and Norwegian seas (Nordic Sea). This is the first time that a comprehensive d18OCib data set is generated and compiled from the Arctic Ocean. For comparison, we defined Atlantic Water (AW), upper Arctic Bottom Water (uABW), and Arctic Bottom Water (ABW) by their temperature/salinity characteristics and calculated mean equilibrium calcite d18Oequ from summer sea-water d18Ow and in situ temperatures. As a result, in the Arctic environment we compensate for Cibicidoides- and Cibicides-specific offsets from equilibrium calcite of -0.35 and -0.55 per mil, respectively. After this taxon-specific adjustment, mean d18OCib values plausibly reflect the density stratification of principle water masses in the Nordic Sea and Arctic Ocean. In addition, mean d18OCib from AW not only significantly differs from mean d18OCib from ABW, but also d18OCib from within AW differentiates in function of provenience and water mass age. Furthermore, in shallow waters brine-derived low d18Ow can significantly lower the d18OCib of Cibicides spp. and thus d18OCib may serve as a paleobrine indicator. There is no statistically significant difference, however, between deeper water masses mean d18OCib of the Nordic Sea, and of the Eurasian and Amerasian basins, and no influence of low-d18Ow brines is recorded in Recent uABW and ABW d18OCib of C. wuellerstorfi. This may be due to dilution of a low-d18Ow brine signal in the deep sea, and/or to preferential incorporation of relatively high-d18Ow brines from high-salinity shelves. Although our data encompass environments with seasonal sea-ice and brine formation supposed to ultimately ventilate the deep Arctic Ocean, d18OCib from uABW and ABW do not indicate negative excursions. This may challenge hypotheses that call for enhanced Arctic brine release to explain negative benthic d18O spikes in deep-sea sediments from the late Pleistocene North Atlantic Ocean.

Stable isotope record of DSDP Hole 81-552A in the northeastern Atlantic Ocean

Oxygen and carbon isotope ratios in benthic foraminifers have been determined at 10 cm intervals through the top 59 m of DSDP Hole 552A. This provides a glacial record of remarkable resolution for the late Pliocene and Pleistocene. The major glacial event which marked the onset of Pleistocene-like glacial-interglacial alternations was at about 2.4 m.y. ago. These very high-resolution data do not support the notion of significant Northern Hemisphere glaciation between 3.2 and 2.4 m.y. ago.

Stable isotope record of foraminifera from ODP Hole 114-704A

Isotopic and sedimentologic data from Ocean Drilling Program hole 704A suggest that isotopic stages 7, 9, and 11 were marked by unusually strong interglacial conditions in surface waters of the southern ocean. During interglacial stages 9 and 11, warm surface waters penetrated far poleward and may have led to destabilization of the West Antarctic Ice Sheet. In contrast, the strongest glacial conditions in surface waters of the subantarctic South Atlantic occurred during oxygen isotopic stage 12. Comparisons of benthic carbon isotopic gradients between sites located in the North Atlantic, southern ocean, and Pacific indicate that the production of upper North Atlantic Deep Water (uNADW) was strongest during stages 7,9, and 11 and weakest during stage 12, These results suggest a possible link between the flux of uNADW and paleoceanographic change in the southern ocean and support the traditional NADW-Antarctic connection whereby increased NADW leads to warming of the southern ocean.

Quaternary carbonate and stable isotope record of ODP Holes 133-817A and 133-818B

The Quaternary history of metastable CaCO3 input and preservation within Antarctic Intermediate Water (AAIW) was examined by studying sediments from ODP Holes 818B (745 mbsl) and 817A (1015 mbsl) drilled in the Townsville Trough on the southern slope of the Queensland Plateau. These sites lie within the core of modern AAIW, and near the aragonite saturation depth (~1000 m). Thus, they are well positioned to monitor chemical changes that may have occurred within this watermass during the past 1.6 m.y. The percent of fine aragonite content, percent of fine magnesian calcite content, and percent of whole pteropods (>355 µm) were used to separate the fine aragonite input signal from the CaCO3 preservation signal. Stable d18O and d13C isotopic ratios were determined for the planktonic foraminifer Globigerinoides sacculifer and, in Hole 818B, for the benthic foraminifer Cibicidoides spp. to establish the oxygen isotope stratigraphy and to study the relationship between intermediate and shallow water d13C of Sum CO2 and the relationship between benthic foraminiferal d13C and CaCO3 preservation within intermediate waters of the Townsville Trough. Data were converted from depth to age using oxygen isotope stratigraphy, nannostratigraphy, and foraminiferal biostratigraphy. Several long hiatuses and the absence of magnetostratigraphy did not permit time series analysis. The principal results of the CaCO3 preservation study include the following (1) a general increase in CaCO3 preservation between 0.9 and 1.6 Ma; (2) a CaCO3 dissolution maximum near 0.9 Ma, primarily expressed in the Hole 818B fine aragonite record; (3) an abrupt and permanent increase of fine aragonite content between 0.86 and 0.875 Ma in both Holes 818B and 817A probably reflecting a dramatic increase of fine carbonate sediment production on the Queensland Plateau; (4) an improvement in CaCO3 preservation near 0.87 Ma, which accompanied the increase of sediment input, indicated by the first appearance of whole pteropods in the deeper Hole 817A and a "spike" in the percent whole pteropods in Hole 818B; (5) a period of strong CaCO3 dissolution during the mid-Brunhes Chron from 0.36 to 0.41 Ma; and (6) a complex CaCO3 preservation pattern between 0.36 Ma and the present characterized by a general increase in CaCO3 preservation through time with good preservation during interglacial stages and poor preservation during glacial stages. The long-term aragonite preservation histories for Holes 818B and 817A appear to be similar in general shape, although different in detail, to CaCO3 preservation records from the deep Indian and central equatorial Pacific oceans as well as from intermediate water sites in the Bahamas and the Maldives. All of these areas have experienced CaCO3 dissolution at about 0.9 Ma and during the mid-Brunhes Chron. However, the late Quaternary (0 to 0.36 Ma) glacial to interglacial preservation pattern in Holes 818B and 817A is out of phase with CaCO3 preservation records for sediments deposited in Pacific deep and bottom waters. The sharp increase in bank production and export from the Queensland Plateau and the coincident improvement of CaCO3 preservation between 0.86 and 0.875 Ma may have been synchronous with the initiation of the Great Barrier Reef and roughly coincides with an increase in carbonate accumulation on the Bahama banks, in the western North Atlantic Ocean, and on Mururoa atoll, in the central South Pacific Ocean. The development of these reef systems during the middle Quaternary may be related to the transition in the frequency and amplitude of global sea level change from 41 k.y. low amplitude cycles prior to 0.9 Ma to 100 k.y. high amplitude cycles after 0.73 Ma. Carbon isotopic analyses show that benthic foraminiferal d13C values (Cibicidoides spp.) have been heavier than planktonic foraminiferal d13C values (G. sacculifer) throughout most of the last 0.54 m.y., which may indicate that 13C-enriched intermediate water (AAIW) occupied the Townsville Trough during much of the late Quaternary. Furthermore, both planktonic and benthic foraminiferal d13C values are often observed to be heaviest during interglacial to glacial transitions, and lightest during glacial to interglacial transitions. We suggest that this pattern is the result of changes in the preformed d13C of Sum CO2 of AAIW and may reflect changes in nutrient utilization by primary producers in Antarctic surface waters, changes in the d13C of upwelled Circumpolar Deep Water, or changes in the extent and/or temperature of equilibration between surface water and atmospheric CO2 within the Antarctic Polar Frontal Zone (the source area for AAIW). Finally, the poor correlation between percent of whole pteropods (aragonite preservation) and d13C of Cibicidoides spp. may be the result of a decoupling of d13C from CO2 due to the numerous and complex variables that combine to produce the preformed d13C of AAIW.