(Table 4) Estimated surface water phosphate concentrations for the past 200 kyr at the location of sediment core GeoB1016-3

We compared ocean atlas values of surface water [PO4]3- and [CO2(aq)] against the carbon isotopic fractionation (ep) of alkenones obtained from surface sediments of the South Atlantic and the central Pacific (Pacific data are from Pagani et al. 2002, doi:10.1029/2002PA000756). We observed a positive correlation between ep and 1/[CO2(aq)], which is opposite of what would be expected if the concentration of CO2(aq) were the major factor controlling the carbon isotopic fractionation of C37:2 alkenones. Instead, we found inverse relationships between ep and [PO4]3- for the two ocean basins (for the Atlantic, ep = -4.6*[PO4]3- + 15.1, R = 0.76; for the Pacific, ep = -4.1*[PO4]3- + 13.7, R = 0.64), suggesting that ep is predominantly controlled by growth rate, which in turn is related to nutrient concentration. The similarity of the slopes implies that a general relationship between both parameters may exist. Using the relationship obtained from the South Atlantic, we estimated surface water nutrient concentrations for the past 200,000 years from a deep-sea sediment core recovered off Angola. Low ep values, indicating high nutrient concentrations, coincide with high contents of total organic carbon and C37 alkenones, low surface water temperatures, and decreased bulk d15N values, suggesting an increased upwelling of nutrient-rich cool subsurface waters as the main cause for the observed ep decrease.

Paleotemperatures, stable isotopes and alkenones of samples from the South Atlantic

Carbon dioxide is one of the most important greenhouse gases which are increasing in atmospheric concentration due to human activities. For using natural CO2 dynamics as a key to understanding the climatic consequences of anthropogenic pCO2 rise, the ocean plays an important role due to its much larger carbon pool compared to the atmosphere. By studying the ratio of stable carbon isotopes in organic matter from marine sediments, it is possible to estimate the partial pressure of CO2 in surface waters during ancient times. The organic compound C37:2 alkenone, whose sole origin is from autotrophic marine algae, was chosen for d13C analysis and its isotopic composition used to reconstruct past PCO2 levels in the surface layer of the eastern Angola Basin for the last 200,000 years. In addition to the variation of ancient concentrations of dissolved CO2 ([CO2(aq)] = ce), the effect of carbon demand which depends on algal growth rate was considered. Here to, carbon isotopic fractionation of C37:2 alkenones (ep) in core-top sediments from the equatorial and the South Atlantic was calibrated against pre-industrial [CO2(aq)] and phosphate concentrations in surface waters. From these data, a variable b = (25 per mil - ep) * ce which reflects intracellular carbon demand was calculated. This variable b correlates with the ambient concentration of seawater phosphate and depends on growth rates. The bulk sediment d15N was used as a proxy parameter for calculating ancient b-values, taking into account that d15N in core-top sediments is correlated to phosphate concentration in modern surface waters. On this basis, the alkenone d13C record of GeoB1016-3 documents a permanent oceanic source for atmospheric carbon dioxide during the last 200,000 years. As a consequence of using d15N derived b-values instead of b = constant, the Angola Basin appears to have been an even stronger CO2 source during glacial periods than at present. Qualitatively similar results were reported by Jasper et al. (1994) for the central Equatorial Pacific. These observations suggest that enhanced productivity of low-latitude upwelling areas during glacial periods is not responsible for the lower CO2 content of the glacial atmosphere.

Plant-wax, alkenone and major element analyses of ODP Site 659 for the Last Glacial cycle and associated coretop data

We present a hydrologic reconstruction of the Sahara-Sahel transition, covering the complete last glacial cycle (130 ka), based on a combination of plant-wax-specific hydrogen (dD) and carbon isotopes (d13C). The dD and d13C signatures of long-chain n-alkanes from ODP Site 659 off NW Africa reveal a significant anti-correlation. Complementary to published pollen data, we infer that this plant-wax signal reflects sensitive responses of the vegetation cover to precipitation changes in the Sahel region, as well as varying contributions from biomes north of the Sahara (C3 domain) by North-East Trade Winds (NETW). During arid phases, especially the northern parts of the Sahel likely experienced crucial water stress, which resulted in a pronounced contraction of the vegetation cover, thus reducing the amount of C4 plant waxes from the region. The increase in NETW strength during dry periods further promoted a more pronounced C3-plant-wax signal derived from the North African C3 plant domain. During humid periods, the C4-dominated Sahelian environments spread northward into the Saharan realm, in association with lower NETW inputs of C3 plant waxes. Arid-humid cycles deduced from plant-wax dD are in accordance with concomitant changes in weathering intensity reflected in varying major element distributions. Environmental shifts are generally linked to periods with large fluctuations in Northern Hemisphere summer insolation. During Marine Isotope Stages 2 and 3, when insolation variability was low, coupling of the hydrologic regime to alkenone-based estimates of NE Atlantic sea-surface temperatures becomes apparent.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Alkenone analyses of sediment cores from the western Arabian Sea

Records of total organic carbon (TOC) and C37 alkenones were used as indicators for past primary productivity in the western and eastern Arabian Sea. Data from GeoB 3005, an open ocean site in the western Arabian Sea upwelling area, are compared with similar records of GeoB 3007 from the Owen Ridge, Ocean Drilling Program (ODP) Site 723 from the continental margin off Oman and MD 900963 from the eastern Arabian Sea. TOC/C37 alkenone records together with other proxies used to reconstruct upwelling intensity, indicate periods of high productivity in tune with precessional forcing all over the Arabian Sea. Based on their phase-relationship to variations in boreal summer insolation they can be divided into three groups. In the western Arabian Sea the precession-related phasing is different between productivity proxies and those for summer monsoon wind strength and upwelling intensity. TOC and C37 alkenone records from the western Arabian Sea lag the other monsoonal indicators by about 5 kyr, but lead productivity indicators from the eastern Arabian Sea by 3 kyr. Based on the differences in phase relationships associated with the precessional cycling between productivity and monsoonal proxies in the western Arabian Sea it is proposed that the TOC/C37 alkenone signal in the western Arabian Sea document a combined signal of moderate SW monsoon winds and of strengthened and prolonged NE monsoon winds. In the eastern Arabian Sea the phasing hints to coincidence between maximum productivity and stronger NE monsoon winds associated with precession-related maxima in ice volume. In contrast, variations in paleoproductivity at site GeoB 3007 from the Owen Ridge indicate productivity maxima during glacial substages 8.2, 6.2 and 2.2, whereas precessionrelated changes are of only minor importance at this location. The results of frequency analyses confirm that productivity at site GeoB 3007 responds predominantly to glacialinterglacial climate changes, while site GeoB 3005 from the open ocean upwelling region near the Gulf of Aden is dominated by precessional insolation. A possible explanation for the pattern revealed at the Owen Ridge is the periodic NW-SE displacement of the Findlater Jet axis, which separates the region of open ocean upwelling to the northwest from downwelling to the southeast ofthe jet. The carbon isotopes of planktic foraminifera reflect nutrient related d13C variations of dissolved inorganic carbon. The difference between the planktic foraminifera Globigerinoides ruber (w), living in the upper 50 m of the water column, and the deeper Iiving Neogloboquadrina dutertrei (Delta d13Cr-d) of core GeoB 3005 displays nutrient variations in the upwelling area near the Gulf of Aden. The results of cross-spectral analyses between Deltad13Cr-d of GeoB 3005 and proxies for SW monsoon intensity indicate, too, a dissociation of productivity from monsoonal upwelling intensity. Instead, productivity depends mainly on the availability of nutrients, while upwelling intensity of sub-surface water masses seems to be of only secondary importance. Additionally, sea surface temperatures (SSTs) were reconstructed using the unsaturation ratio of C37 alkenones. Alkenone SSTs reflect annual mean temperatures rather than explicitly the season of upwelling. This is evident from alkenone SSTs in a transect of surface sediments extending from the inner Gulf of Aden into the western Arabian Sea. The alkenone-derived SST records of GeoB 3005 from the open ocean upwelling region near the Gulf of Aden and GeoB 3007 from the Owen Ridge reveal similar variations with high SSTs during interglacial and low SSTs during glacial periods. The glacial marine oxygen isotope stage (MIS) 6 remains relatively warm and was not as cold as MIS 3 to 4 and 8 according to the alkenone SST. Similar variation-patterns were reconstructed in the coastal upwelling area off Oman for ODP Site 723 as weIl as in the eastern Arabian Sea for MD 900963, where upwelling is not as pronounced as in the western Arabian Sea. Spectral-analyses indicate that SST changes are in good agreement with the modulation of low-latitude precessional insolation changes by eccentricity. However, they do not show the pronounced cydicity in the precessional frequency band, which is characteristic for variations in paleoproductivity. Although the overall variation pattern is very similar, a dose comparison between the western (GeoB 3005) and the eastern Arabian Sea (MD 900963) shows larger differences between both sites during cold intervals than during periods of warm SSTs. This is attributed to a more effective cooling of surface waters in the western Arabian Sea by prolonged NE monsoon winds during times of expanded Northern Hemisphere ice-sheets, thereby lowering the annual mean SSTs stronger than in the eastern Arabian Sea.

Alkenone data of sediment core GeoB9508-5 from the continental slope off Senegal

In order to investigate a possible link between tropical Northeast (NE) Atlantic sea-surface temperature (SST), Atlantic meridional overturning circulation (AMOC), and drought in the Sahel during the past 44 thousand years (kyr) we used alkenone paleothermometry and d13C of C. wuellerstorfi of a marine sediment core from the continental slope off Senegal. Our data show periods of low SST and reduced AMOC that coincided with drought in the Sahel during North Atlantic Heinrich stadials (HS). The coldest period was HS1 (ca. 15-18 kyr before present, BP) when SST decreased by more than 2°C. Moreover, the SST off Senegal lagged variations in Sahel aridity, which is in agreement with results from a freshwater hosing experiment. We conclude that variations in tropical NE Atlantic SST were not the initial trigger of millennial-scale Sahel droughts of the past 44 kyr. Instead, it is thought that these droughts were induced by substantial coolings of the extratropical North Atlantic.

Alkenone stable carbon isotopes, planktic foraminfera stable carbon isotopes, alkenone unsaturation indices and calculated sea surface temperatures and atmospheric pCO2 for ODP Site 165-999

Temperature reconstructions indicate that the Pliocene was ~3 °C warmer globally than today, and several recent reconstructions of Pliocene atmospheric CO2 indicate that it was above pre-industrial levels and similar to those likely to be seen this century. However, many of these reconstructions have been of relatively low temporal resolution, meaning that these records may have failed to capture variations associated with the 41 Kyr glacial-interglacial cycles thought to operate in the Pliocene. Here we present a new, high temporal resolution alkenone carbon isotope based record of pCO2 spanning 2.8 to 3.3 million years ago from ODP Site 999. Our record is of high enough resolution (~19 Kyrs) to resolve glacial-interglacial changes beyond the intrinsic uncertainty of the proxy method. The record suggests that Pliocene CO2 levels were relatively stable, exhibiting variation less than 55 ppm. We perform sensitivity studies to investigate the possible effect of changing sea surface temperature, which highlights the importance of accurate and precise SST reconstructions for alkenone palaeobarometry, but demonstrate that these uncertainties do not affect our conclusions of relatively stable pCO2 levels during this interval.