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.

Mineralogy, geochemistry, isotopic ratios and foraminifer occurrence in ODP Hole 183-1139A

Mixed terrigenous-pelagic sediments from the Oligocene-lower Miocene interval of Hole 1139A accumulated on the flank of an eroded alkalic volcano, Skiff Bank. In this study, I explore relationships among sediment fluxes, especially of organic carbon and the clay mineral by-products of silicate weathering, and lithologic, tectonic, climatic, and biologic forcing factors. Benthic foraminifers indicate that Skiff Bank had subsided to lower bathyal depths (1000-2000 m) by the Oligocene. Two prominent maxima in noncarbonate concentration at 28 and 22 Ma correspond to peaks in the terrigenous flux; also, high noncarbonate concentrations are associated with larger grain sizes (silt) and higher opal concentrations. These and higher-frequency variations of noncarbonate concentration were probably controlled by glacioeustatic/climatic changes, with higher noncarbonate concentrations caused by increased erosion during glacial lowstands. Around 27 Ma, benthic foraminiferal d18O values decreased 0.7 per mil as the noncarbonate concentration decreased after the 28-Ma maximum. A paucity of clay-sized sediment and clay minerals suggests that physical erosion, by waves and/or ice, predominated under weathering-limited conditions. Low organic carbon concentrations (~0.13 wt%) also suggest a harsh environment and/or poor preservation in coarse (>2 µm) sediments that were extensively bioturbated below the oxygen minimum zone.

Stable carbon and oxygen isotope ratios of Cibicidoides wuellerstorfi (Table 1)

Here we present the first species-specific study of boron isotopes in the epibenthic foraminifer species Cibicidoides wuellerstorfi. Coretop samples from a water depth profile from 1000 to 4500 m on the northern flank of the Walvis Ridge are 4.4 per mil lower than the values expected, based on calculations of the delta 11B(borate) of ambient seawater. Similar values for this foraminifer species are presented from ODP site 668B at the Sierra Leone Rise, in the equatorial Atlantic. The consistency between data of the same species suggests the offsets are primary, rather than diagenetic. Glacial C. wuellerstorfi from ODP 668B and Walvis Ridge have boron isotope compositions only slightly different to interglacial samples, that is no larger than +0.10 pH units, or +23 µmol/kg in [CO3[2-]] above the reconstructed glacial lysocline, and -0.07 pH units, or -14 µmol/kg in [CO3[2-]] below. We use these results to suggest that glacial deep water pH in the Atlantic was similar to interglacial pH. The new data resolve the inconsistency between the previously reported high bottom water pH and the lack of significant carbonate preservation of the glacial deep ocean.

Stable isotope record of Cibicidoides wuellerstorfi from Pleistocene sediments of DSDP Site 86-502 in the Caribbean Sea

Variations in the stable isotopic composition of benthic foraminifera from Deep-Sea Drilling Project (DSDP) site 502B in the Caribbean Sea are used to reconstruct Atlantic intermediate water circulation variability over the last 1.2 m.y. Comparison of this record with other North Atlantic benthic isotope records indicates that Atlantic intermediate water circulation was relatively enhanced during glacial maxima when North Atlantic deep water (NADW) production was reduced. However, a simple, compensatory relationship between intermediate and deepwater circulation is not apparent. Geochemical models have shown that such changes in ocean circulation can affect atmospheric CO2 levels by changing vertical nutrient and alkalinity profiles. The Delta delta13C difference between Caribbean site 502B and deep equatorial Pacific site 677 is highly coherent and in phase with ice volume. Like the delta18O record, there is an increase in amplitude (40%) and a large increase in 100 kyr power after 0.7 Ma. The 1.2? Delta delta13C amplitude scales to 70 ppm V in atmospheric CO2 using Boyle's (1986) box model result. The implied increase in CO2 amplitude after 0.7 Ma may suggest a positive feedback role in effecting the higher-amplitude climatic fluctuations which characterize the last 0.7 m.y.

Stable isotope ratios of epibenthic foraminifer Cibicidoides wuellerstorfi from sediment profile GeoB9526

Studies of temporal changes of ocean circulation and deep-water ventilation often rely on d13C records of epibenthic foraminifer Cibicidoides wuellerstorfi. However, primary productivity related overprints may distort the signal and simulate a chemical age of ambient water mass that is too old and simulates poorly ventilated ambient bottom waters. To further constrain the use of C. wuellerstorfi d13C records from high-productivity areas, we analyzed a 14CAMS-dated gravity core from the upwelling regime off northwest Africa at 12°N. We compare this new record with 37 radiocarbon dated d13C records from the eastern Atlantic Ocean between 45°N and 25°S that are bathed by the same water mass. Only during Heinrich events 1 and 2, when the investigated core site off northwest Africa experienced year-round, sustained deposition of organic matter, the d13C values at this site faithfully record deep-water ventilation states. During times of predominantly seasonal deposition of fresh phytodetritus, however, d13C values were significantly lower than at the reference sites. This underscores that reconstruction of paleocirculation and deep ocean ventilation using C. wuellerstorfi d13C from regions that experienced seasonal phytodetritus deposition needs to be validated by additional proxies that are not affected by local productivity.