1.2 Ma stacked benthic foraminiferal carbon isotope record

Pleistocene stable carbon isotope (d13C) records from surface and deep dwelling foraminifera in all major ocean basins show two distinct long-term carbon isotope fluctuations since 1.00 Ma. The first started around 1.00 Ma and was characterised by a 0.35 per mil decrease in d13C values until 0.90 Ma, followed by an increase of 0.60 per mil lasting until 0.50 Ma. The subsequent fluctuation started with a 0.40 per mil decrease between 0.50 and 0.25 Ma, followed by an increase of 0.30 per mil between 0.25 and 0.10 Ma. Here, we evaluate existing evidence and various hypotheses for these global Pleistocene d13C fluctuations and present an interpretation, where the fluctuations most likely resulted from concomitant changes in the burial fluxes of organic and inorganic carbon due to ventilation changes and/or changes in the production and export ratio. Our model indicates that to satisfy the long-term 'stability' of the Pleistocene lysocline, the ratio between the amounts of change in the organic and inorganic carbon burial fluxes would have to be close to a 1:1 ratio, as deviations from this ratio would lead to sizable variations in the depth of the lysocline. It is then apparent that the mid-Pleistocene climate transition, which, apart from the glacial cycles, represents the most fundamental change in the Pleistocene climate, was likely not associated with a fundamental change in atmospheric pCO2. While recognising that high frequency glacial/interglacial cycles are associated with relatively large (100 ppmv) changes in pCO2, our model scenario (with burial changes close to a 1:1 ratio) produces a maximum long-term variability of only 20 ppmv over the fluctuation between 1.00 and 0.50 Ma.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Age models for ODP Leg 172 sites

Ten ODP sites drilled in a depth transect (2164-4775 m water depth) during Leg 172 recovered high-deposition rate (>20 cm/kyr) sedimentary sections from sediment drifts in the western North Atlantic. For each site an age model covering the past 0.8-0.9 Ma has been developed. The time scales have a resolution of 10-20 kyr and are derived by tuning variations of estimated carbonate content to the orbital parameters precession and obliquity. Based on the similarity in the signature of proxy records and the spectral character of the time series, the sites are divided into two groups: precession cycles are better developed in carbonate records from a group of shallow sites (2164-2975 m water depth, Sites 1055-1058) while the deeper sites (2995-4775 m water depth, Sites 1060-1063) are characterized by higher spectral density in the obliquity band. The resulting time scales show excellent coherence with other dated carbonate and isotope records from low latitudes. Besides the typical Milankovitch cyclicity significant variance of the resulting carbonate time series is concentrated at millennial-scale changes with periods of about 12, 6, 4, 2.5, and 1.5 kyr. Comparisons of carbonate records from the Blake Bahama Outer Ridge and the Bermuda Rise reveal a remarkable similarity in the time and frequency domain indicating a basin-wide uniform sedimentation pattern during the last 0.9 Ma.

Palaeoceanographic data of sediment core MD01-2416

We present an SiF4 separation line, coupled to a laser fluorination system, which allows for an efficient combined silica d18O and d30Si analysis (50 min per sample). The required sample weight of 1.5-2.0 mg allows for high-resolution isotope studies on biogenic opal. Besides analytical tests, the new instrumentation set-up was used to analyse two marine diatom fractions (>63 µm, 10-20 µm) with different diatom species compositions extracted from a Bølling/Allerød-Holocene core section [MD01-2416, North-West (NW) Pacific] to evaluate the palaeoceanographic significance of the diatom isotopic signals and to address isotopic effects related to contamination and species-related isotope effects (vital and environmental effects). While d30Si offsets between the two fractions were not discernible, supporting the absence of species-related silicon isotope effects, systematic offsets occur between the d18O records. Although small, these offsets point to species-related isotope effects, as bias by contamination can be discarded. The new records strengthen the palaeoceanographic history during the last deglaciation in the NW Pacific characterized by a sequence of events with varying surface water structure and biological productivity. With such palaeoceanographic evolution it becomes unlikely that the observed systematic d18O offsets signal seasonal temperature variability. This calls for reconsideration of vital effects, generally excluded to affect d18O measurements.

Paleoceanography of sediment cores SO202-27-6 and MD01-2416

The glacial-to-Holocene evolution of subarctic Pacific surface water stratification and silicic acid (Si) dynamics is investigated based on new combined diatom oxygen (d18Odiat) and silicon (d30Sidiat) isotope records, along with new biogenic opal, subsurface foraminiferal d18O, alkenone-based sea surface temperature, sea ice, diatom, and core logging data from the NE Pacific. Our results suggest that d18Odiat values are primarily influenced by changes in freshwater discharge from the Cordilleran Ice Sheet (CIS), while corresponding d30Sidiat are primarily influenced by changes in Si supply to surface waters. Our data indicate enhanced glacial to mid Heinrich Stadial 1 (HS1) NE Pacific surface water stratification, generally limiting the Si supply to surface waters. However, we suggest that an increase in Si supply during early HS1, when surface waters were still stratified, is linked to increased North Pacific Intermediate Water formation. The coincidence between fresh surface waters during HS1 and enhanced ice-rafted debris sedimentation in the North Atlantic indicates a close link between CIS and Laurentide Ice Sheet dynamics and a dominant atmospheric control on CIS deglaciation. The Bølling/Allerød (B/A) is characterized by destratification in the subarctic Pacific and an increased supply of saline, Si-rich waters to surface waters. This change toward increased convection occurred prior to the Bølling warming and is likely triggered by a switch to sea ice-free conditions during late HS1. Our results furthermore indicate a decreased efficiency of the biological pump during late HS1 and the B/A (possibly also the Younger Dryas), suggesting that the subarctic Pacific has then been a source region of atmospheric CO2.

Stable oxygen isotope. Mg/Ca and Temperature record of Caribbean and Pacific sediments

The final phase of the closure of the Panamanian Gateway and the intensification of Northern Hemisphere Glaciation (NHG) both occurred during the Late Pliocene. Glacial-interglacial (G-IG) variations in sea level might, therefore, have had a significant impact on the remaining connections between the East Pacific and the Caribbean. Here, we present combined foraminiferal Mg/Ca and d18O measurements from Ocean Drilling Program (ODP) Site 1241 from the East Pacific and ODP Site 999 from the Caribbean. The studied time interval covers the first three major G-IG Marine Isotope Stages (MIS 95-100, ~2.5 Ma) after the intensification of NHG. Analyses were performed on the planktonic foraminifera Neogloboquadrina dutertrei and Globigerinoides sacculifer, representing water mass properties in the thermocline and the mixed-layer, respectively. Changes in sea water temperature, relative salinity, and water column stratification strongly suggest that the Panamanian Gateway temporarily closed during glacial MIS 98 and 100, as a result of changes in ice volume equivalent to a drop in sea level of 60-90 m. Reconstructed sea surface temperatures (SST) from G. sacculifer show a glacial decrease of 2.5°C at Site 1241, but increases of up to 3°C at Site 999 during glacial MIS 98 and 100 suggesting that the Panamanian Gateway closed during these glacial periods. The Mg/Ca-temperatures of N. dutertrei remain relatively stable in the East Pacific, but do show a 3°C warming in the Caribbean at the onset of these glacial periods suggesting that the closing of the gateway also changed the water column stratification. We infer that the glacial closure of the gateway allowed the Western Atlantic Warm Pool to extend into the southern Caribbean, increasing SST (G. sacculifer) and deepening the thermocline (N. dutertrei). Additionally, ice volume appears to have become large enough during MIS 100 to survive the relatively short lasting interglacial MIS 99 so that the gateway remained closed. Towards the end of MIS 98, during MIS 97 and into MIS 96 temperatures on both sides are mostly similar suggesting water masses exchanged again. Additionally, Caribbean variations in SST and d18Owater follow a precession-like cyclicity rather than the obliquity-controlled variations characteristic of the East-Pacific and many other tropical areas, suggesting that regional atmospheric processes related to the trade winds and the Intertropical Convergence Zone (ITCZ) had a dominant impact in the Caribbean.

Radiocarbon ages and stable isotope measurements on sediment cores of the subarctic Pacific and its marginal seas

Under modern conditions only North Pacific Intermediate Water is formed in the northwest Pacific Ocean. This situation might have changed in the past. Recent studies with general circulation models indicate a switch to deep-water formation in the northwest Pacific during Heinrich Stadial 1 (17.5-15.0 ka) of the last glacial termination. Reconstructions of past ventilation changes based on paleoceanographic proxy records are still insufficient to test whether a deglacial mode of deep-water formation in the North Pacific Ocean existed. Here we present deglacial ventilation records based on radiocarbon-derived ventilation ages in combination with epibenthic stable carbon isotopes from the northwest Pacific including the Okhotsk Sea and Bering Sea, the two potential source regions for past North Pacific ventilation changes. Evidence for most rigorous ventilation of the intermediate-depth North Pacific occurred during Heinrich Stadial 1 and the Younger Dryas, simultaneous to significant reductions in Atlantic Meridional Overturning Circulation. Concurrent changes in d13C and ventilation ages point to the Okhotsk Sea as driver of millennial-scale changes in North Pacific Intermediate Water ventilation during the last deglaciation. Our records additionally indicate that changes in the d13C intermediate-water (700-1750 m water depth) signature and radiocarbon-derived ventilation ages are in antiphase to those of the deep North Pacific Ocean (>2100 m water depth) during the last glacial termination. Thus, intermediate- and deep-water masses of the northwest Pacific have a differing ventilation history during the last deglaciation.

Log-ratio of silica to aluminium counts (ln(Si/Al)) from ODP site 108-658

Growing evidence suggests that the low atmospheric CO2 concentration of the ice ages resulted from enhanced storage of CO2 in the ocean interior, largely as a result of changes in the Southern Ocean1. Early in the most recent deglaciation, a reduction in North Atlantic overturning circulation seems to have driven CO2 release from the Southern Ocean**2, 3, 4, 5, but the mechanism connecting the North Atlantic and the Southern Ocean remains unclear. Biogenic opal export in the low-latitude ocean relies on silicate from the underlying thermocline, the concentration of which is affected by the circulation of the ocean interior. Here we report a record of biogenic opal export from a coastal upwelling system off the coast of northwest Africa that shows pronounced opal maxima during each glacial termination over the past 550,000 years. These opal peaks are consistent with a strong deglacial reduction in the formation of silicate-poor glacial North Atlantic intermediate water**2 (GNAIW). The loss of GNAIW allowed mixing with underlying silicate-rich deep water to increase the silicate supply to the surface ocean. An increase in westerly-wind-driven upwelling in the Southern Ocean in response to the North Atlantic change has been proposed to drive the deglacial rise in atmospheric CO2 (refs 3, 4). However, such a circulation change would have accelerated the formation of Antarctic intermediate water and sub-Antarctic mode water, which today have as little silicate as North Atlantic Deep Water and would have thus maintained low silicate concentrations in the Atlantic thermocline. The deglacial opal maxima reported here suggest an alternative mechanism for the deglacial CO2 release**5, 6. Just as the reduction in GNAIW led to upward silicate transport, it should also have allowed the downward mixing of warm, low-density surface water to reach into the deep ocean. The resulting decrease in the density of the deep Atlantic relative to the Southern Ocean surface promoted Antarctic overturning, which released CO2 to the atmosphere.