Major and trace elements and interelement ratios at DSDP Leg 81 Holes

Fifty-two samples of basalt from the four holes drilled on the Leg 81 transect across the Rockall margin were analyzed by X-ray fluorescence for Rb, Sr, Y, Zr, and Nb. On the basis of these results 13 samples were chosen for major and supplementary trace-element analysis. The results show no progressive change in the character of the volcanism, from Hole 555 in the continental domain through Holes 552 and 553A in the dipping reflector sequence to Hole 554A on the outer high. Two distinct magma types are present, apparently reflecting heterogeneity of the underlying mantle, but both types are present in both Holes 553A and 555, while Hole 552 and Hole 554 are each composed of a single type. Both magma types have a clear ocean-floor basalt signature when examined by discrimination diagrams, as does the basalt from Deep Sea Drilling Project Site 112, which formed at the same time as the Leg 81 basalts slightly farther south along the spreading center. In contrast, the basalts of East Greenland, formed at the same time, are more enriched in incompatible elements and have a within-plate geochemical signature, as is found in some basalts of Iceland today. Clearly the present distinction in geochemistry between the basalts of Iceland and those erupting well south on the Reykjanes Ridge was already established when continental splitting took place.

Age determination and stable isotope ratios of three sediment cores from the Great Belt

The marine transgression Into the Baltic Sea through the Great Belt took place around 9,370 calibrated C-14-years B.P. The sedimentary sequence from the early brackish phase and the change to marine conditions has been investigated in detail through C-14-datings, and oxygen and carbon isotope measurements, and is interpreted by comparison with modern analogs. The oldest brackish sediments are the strongly laminated clays and silts rich in organic carbon followed by non-laminated heavily bioturbated silts. The bedding and textural characteristics and stable isotope analyses on Ammonia beccarii (dextral) and A. beccarii (sinistral) show that the deposltlonal conditions respond to a change at about 9,100 cal. a B.P. from an unstratified brackish water environment in the initial stage of the Littorina Transgression to a thermohaline layered milieu in the upper unit. The oxygen isotope results indicate that the bottom waters of this latter period had salinities and temperatures comparable to the present day Kiel Bay waters. The isotopic composition of the total organic carbon and the d13C-values of A. beccarii reveal a gradual change from an initially lacustrine/terrestrial provenance toward a brackish/marine dominated depositional environment. A stagnation of the sea level at around 9,100 to 9,400 B.P. is indicated.

Compilation of 231Protactinium/230 Thorium excess ratios in various surface sediment samples from the South Atlantic

In large areas of the world's oceans, there is a relationship between the mass flux of particulate matter and the unsupported 231Pa/230Th (xs231Pa/xs230Th) activity ratio of recent sediments. This observation forms the basis for using the xs231Pa/xs230Th ratio as a proxy for past changes in export productivity. However, a simple relationship between xs231Pa/xs 230Th ratio and particle flux requires that the water residence time in an ocean basin is far in excess of the scavenging residence time of 231Pa, and that the composition of sinking particles maintains a strong preference for the adsorption of 230Th over 231Pa with a constant 230Th/231Pa fractionation factor (F). The best correlation between xs231Pa/xs230Th ratio and mass flux is found in the Pacific Ocean. In the Atlantic, the contrast in the xs231Pa/xs230Th ratios between open ocean (low flux regions) and ocean margins (high flux regions) is much less pronounced due to the shorter residence time of deep water, resulting in less effective boundary scavenging of 231Pa. In the Southern Ocean, south of the Polar Front, there is no more a simple relationship between xs231Pa/xs230Th and particle flux. This is a result of a southward decrease in F, probably reflecting the increased opal content of sinking particles. Opal does not fractionate 231Pa and 230Th significantly. This lack of fractionation results in high xs231Pa/xs230Th ratios in opal-dominated regions, even in areas of very low particle fluxes such as the Weddell Sea. The xs231Pa/xs230Th ratio can therefore only be used as a paleoproductivity proxy if, in the time interval of interest, changes in the basin ventilation rate and differential scavenging of both radionuclides due to changes in the chemical composition of particulate matter can be excluded.

Age model, lipids, and iron/calcium-ratios of sediment core GeoB9307-3

Hide Intense debate persists about the climatic mechanisms governing hydrologic changes in tropical and subtropical southeast Africa since the Last Glacial Maximum, about 20,000 years ago. In particular, the relative importance of atmospheric and oceanic processes is not firmly established. Southward shifts of the intertropical convergence zone (ITCZ) driven by high-latitude climate changes have been suggested as a primary forcing, whereas other studies infer a predominant influence of Indian Ocean sea surface temperatures on regional rainfall changes. To address this question, a continuous record representing an integrated signal of regional climate variability is required, but has until now been missing. Here we show that remote atmospheric forcing by cold events in the northern high latitudes appears to have been the main driver of hydro-climatology in southeast Africa during rapid climate changes over the past 17,000 years. Our results are based on a reconstruction of precipitation and river discharge changes, as recorded in a marine sediment core off the mouth of the Zambezi River, near the southern boundary of the modern seasonal ITCZ migration. Indian Ocean sea surface temperatures did not exert a primary control over southeast African hydrologic variability. Instead, phases of high precipitation and terrestrial discharge occurred when the ITCZ was forced southwards during Northern Hemisphere cold events, such as Heinrich stadial 1 (around 16,000 years ago) and the Younger Dryas (around 12,000 years ago), or when local summer insolation was high in the late Holocene, i.e., during the last 4,000 years.

Mg/Ca ratios of Globigerinoides ruber of sediment core GeoB4905-4

Here we present evidence that the Holocene African monsoon system (AMS) varied in response to the eastern equatorial Atlantic sea-surface temperature (SST). Several short-term episodes of decreased moisture availability as a result of low eastern equatorial Atlantic SST are suggested by planktonic foraminiferal Mg/Ca ratios. These episodes promoted a weakening of the AMS and thus determined the timing and intensity of arid periods. Local sea-surface salinities also reveal regional patterns of precipitation in equatorial western Africa. The high eastern equatorial Atlantic SSTs occur in concert with seasonally increased insolation at low latitudes, suggesting a strong response of African monsoonal precipitation to oceanic conditions at low latitudes.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Stable isotope ratios and organic carbon accumulation rates of late Pleistocene sediments of ODP Hole 117-724C

Stable isotope records of coexisting benthic foraminifers Uvigerina spp. and Cibicidoides spp. and planktonic G. ruber (white variety) from Site 724 are used to study the late Pleistocene evolution of surface and intermediate water hydrography (593 m water depth) at the Oman Margin. Glacial-interglacial d18O amplitudes recorded by the benthic foraminifers are reduced when compared to the estimated mean ocean changes of d18Oseawater . Epibenthic d13C remains at its modern level or is increased during glacial times. This implies that Red Sea outflow waters which are enriched in d18Oseawater and d13C (Sum CO2) have been replaced during glacial periods by intermediate waters still positive in d13C (Sum CO2) but more negative in d18Oseawater. Glacial-interglacial amplitudes of the planktonic d18O record exceed those of the mean ocean d18Oseawater variation and imply decreased surface water temperatures (SST) during glacial times. Throughout most of the records these cooling events correlate with enhanced rates of carbon accumulation. However, both negative (colder) SST and positive Corg accumulation rate anomalies do not correlate with potential physical upwelling maxima as inferred from the orbital monsoon index. This is in conflict with the established hypothesis that upwelling in the estern Arabia Sea should be strongest during maxima of the southwest monsoon.

Global compilation of last glacial maximum oxygen isotopic ratios for planktonic and benthic foraminifera

We use the fully coupled atmosphere-ocean three-dimensional model of intermediate complexity iLOVECLIM to simulate the climate and oxygen stable isotopic signal during the Last Glacial Maximum (LGM, 21 000 yr). By using a model that is able to explicitly simulate the sensor (d18O), results can be directly compared with data from climatic archives in the different realms. Our results indicate that iLOVECLIM reproduces well the main feature of the LGM climate in the atmospheric and oceanic components. The annual mean d18O in precipitation shows more depleted values in the northern and southern high latitudes during the LGM. The model reproduces very well the spatial gradient observed in ice core records over the Greenland ice-sheet. We observe a general pattern toward more enriched values for continental calcite d18O in the model at the LGM, in agreement with speleothem data. This can be explained by both a general atmospheric cooling in the tropical and subtropical regions and a reduction in precipitation as confirmed by reconstruction derived from pollens and plant macrofossils. Data-model comparison for sea surface temperature indicates that iLOVECLIM is capable to satisfyingly simulate the change in oceanic surface conditions between the LGM and present. Our data-model comparison for calcite d18O allows investigating the large discrepancies with respect to glacial temperatures recorded by different microfossil proxies in the North Atlantic region. The results argue for a trong mean annual cooling between the LGM and present (>6°C), supporting the foraminifera transfer function reconstruction but in disagreement with alkenones and dinocyst reconstructions. The data-model comparison also reveals that large positive calcite d18O anomaly in the Southern Ocean may be explained by an important cooling, although the driver of this pattern is unclear. We deduce a large positive d18Osw anomaly for the north Indian Ocean that contrasts with a large negative d18Osw anomaly in the China Sea between the LGM and present. This pattern may be linked to changes in the hydrological cycle over these regions. Our simulation of the deep ocean suggests that changes in d18Osw between the LGM and present are not spatially homogenous. This is supported by reconstructions derived from pore fluids in deep-sea sediments. The model underestimates the deep ocean cooling thus biasing the comparison with benthic calcite d18O data. Nonetheless, our data-model comparison support a heterogeneous cooling of few degrees (2-4°C) in the LGM Ocean.

Stable isotope record and trace element ratios of Eocene and Oligocene foraminifers from ODP Site 120-748

Stable carbon and oxygen isotope analyses were conducted on well-preserved planktonic and benthic foraminifers from a continuous middle Eocene to Oligocene sequence at Ocean Drilling Program (ODP) Site 748 on the Kerguelen Plateau. Benthic foraminifer d18O values show a 1.0 per mil increase through the middle and upper Eocene, followed by a rapid 1.2 per mil increase in the lowermost Oligocene (35.5 Ma). Surface-dwelling planktonic foraminifer d18O values increase in the lowermost Oligocene, but only by 0.6 per mil whereas intermediate-depth planktonic foraminifers show an increase of about l.0 per mil. Benthic foraminifer d13C values increase by 0.9 per mil in the lowermost Oligocene at precisely the same time as the large d18O increase, whereas planktonic foraminifer d13C values show little or no change. Site 748 oxygen isotope and paleontological records suggest that southern Indian Ocean surface and intermediate waters underwent significant cooling from the early to late Eocene. The rapid 1.2 per mil oxygen isotope increase recorded by benthic foraminifers just above the Eocene/Oligocene boundary represents the ubiquitous early Oligocene d18O event. The shift here is unique, however, as it coincided with the sudden appearance of ice-rafted debris (IRD), providing the first direct link between Antarctic glacial activity and the earliest Oligocene d18O increase. The d18O increase caused by the ice-volume change in the early Oligocene is constrained by (1) related changes in the planktonic to benthic foraminifer d18O gradient at Site 748 and (2) comparisons of late Eocene and early Oligocene planktonic foraminifer d18Ovalues from various latitudes. Both of these records indicate that 0.3 per mil to 0.4 per mil of the early Oligocene d18O increase was ice-volume related.

Age models and stable isotope ratios of SO12 and SO35 sediment cores

Based on organic carbon accumulation rates, nine time slices of oceanic export paleoproductivity (Pnew) are presented which depict the variability of Pnew on a global scale through the last 30,000 years and document that the basic distribution patterns did not change through glacial and interglacial times. However, the glacial ocean shows an increased contrast of high- versus low-productivity zones. d13C values of near-surface-dwelling planktonic foraminifera Globigerinoides ruber suggest that the same contrast applies to the glacial nutrient inventories of the ambient surface waters, with a significant glacial transfer of PO4 from low- to high-productivity zones. In this way, glacial Pnew increased by a global average of about 2-4 Gt C/yr and led, via an enhanced CaCO3 dissolution and alkalinity in the deep ocean, to a significant extraction of CO2 from the surface water and the atrnosphere.