ALBERT

Description: We investigated the controls of hydrography and of scavenging on the distribution of the particle reactive radionuclides 231Pa and 230Th in the water column and in surface sediments off Southwest Africa (Angola and Cape basins). Based on a vertical section of total 230Thex concentrations in the water column we show that small differences in the salinity between the North Atlantic Deep Water (NADW) in the Angola Basin and the NADW in the Cape Basin as well as the advection of NADW associated with the Namib Col Current are reflected in total 230Thex concentrations. These variable total concentrations are believed to reflect the flow path and mixing history of NADW with the NADW in the Angola Basin being relatively older and 230Th enriched compared to the NADW in the Cape Basin. In the area investigated we found high 231Paex/230Thex ratios (231Paex/230Thex 〉 0.093) in surface sediments at the continental margin and lower ones (231Paex/230Thex 〈 0.093) in the open ocean. Such a distribution is normally interpreted to result from high particle flux at ocean margins (boundary scavenging). However, the lack of any significant depletion of dissolved 230Th and 231Pa in the water column does not indicate extensive scavenging at the continental margin. High 231Paex/230Thex ratios are constrained to shallow waters depths (〈 2000 m) only and coincide with low fractionation between 231Pa and 230Th indicating that preferential scavenging of 231Pa on opal may have caused high 231Paex/230Thex ratios in the sediments. The observed close negative correlation (r2 = 0.82) between 231Paex/230Thex ratios in sediments and water depths is believed to reflect changes in the particle composition, i.e. a decrease in opal content with water depth. In the Angola and Cape basins the total 231Paex concentrations in NADW were the highest observed so far in the Atlantic Ocean, and they are attributed to the meridional export of 231Pa from the North Atlantic. This caused the average dissolved 231Pa/230Th in the Southeast Atlantic to be about a factor 2 higher when compared to the North Atlantic (Labrador Sea). These differences in the dissolved 231Pa/230Th were not reflected in 231Pa/230Th ratios of surface sediments because the fractionation is lower in the Labrador Sea compared to the Southeast Atlantic, i.e. fractionation counteracts changes in the dissolved 231Pa/230Th. This suggests that fractionation is more important for the determination of 231Paex/230Thex ratios in sediments than the meridional export of 231Pa from the North Atlantic.

Description: Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Description: We present time series of export productivity proxy data including 230Thex-normalized deposition rates (rain rates) of 10Be, dissolution-corrected biogenic Ba, and biogenic opal as well as authigenic U concentrations which are complemented by rain rates of total (detrital) Fe and sea ice indicating diatom abundances from five sediment cores across the Atlantic sector of the Southern Ocean covering the past 150,000 years. The results suggest that 10Be rain rates and authigenic U concentration cannot serve as quantitative paleoproductivity proxies because they have also been influenced by detrital particle fluxes in the case of 10Be and bulk sedimentation rates (sediment focussing) and deep water oxygenation in the case of U. The combined results of the remaining productivity proxies of this study (rain rates of biogenic opal and biogenic Ba in those sections without authigenic U) and other previously published proxy data from the Southern Ocean (231Pa/230Th and nitrogen isotopes) suggest that a combination of sea ice cover, shallow remineralization depth, and stratification of the glacial water column south of the present position of the Antarctic Polar Front and possibly Fe fertilization north of it have been the main controlling factors of export paleoproductivity in the Southern Ocean over the last 150,000 years. An overall glacial increase of export paleoproductivity is not supported by the data, implying that bioproductivity variations in the Southern Ocean are unlikely to have contributed to the major glacial atmospheric CO2 drawdown observed in ice cores.

Description: Oceanic and atmospheric circulation patterns varied considerably during the Tertiary and Quaternary and influenced the geochemical cycles of elements in seawater. We report the first resolution lead and neodymium isotopic record of such changes at a high time resolution in two depths profiles from a hydrogenous FeMn crust. The crust, Va13-2, is located in the central Pacific (146°W, 9°25′N, 4830 m) and has previously been dated by 230Th and 10Be. The first profile was drilled with a sample time resolution of ∼3 kyr and allows evaluation of short-term changes to lead and neodymium sources to central Pacific seawater over the last 400 kyr (marine δ18O stages 2 to 11). Longer-term changes were monitored at lower time resolution in a second profile to an age of 10 Ma. Short-term variations in lead and neodymium isotope ratios are resolved in the high resolution profile (0 to 400 kyr). Superimposed on the short-term variations is a secular decrease in Full-size image (〈1 K) ratios beginning at ∼130 kyr in marine δ18O stage 5, implying a change in the lead sources to the central Pacific. Lead and neodymium isotopic compositions indicate an increased influence from Central American eolian sources to Pacific seawater at this time. Lead isotopes are found to be statistically more variable during interglacial than glacial periods. These observations are supported by the greater eolian dust fluxes found in sediment cores from the equatorial Pacific during interglacial stages. The most important paleoceanographic event of the last 10 Ma to affect Pacific seawater was the closure of the Panama gateway. Changes in lead and neodymium isotopes in Val3-2 during the last 10 Ma occurred along with gradual closure of the Panama straits. However, these changes did not occur in tandem: while neodymium isotope ratios increase between 10 and 8 Ma, lead isotope ratios remain constant. In contrast, the period 7 to 1 Ma is marked by a secular increase in lead isotope ratios but nearly constant neodymium. These changes are consistent with a source of radiogenic lead and neodymium conveyed by the Circumpolar Current into the Pacific, rather than by the Panama gateway, and involve 20 to 40% Southern Component Water (SCW) input of lead and neodymium. Modelling of lead and neodymium isotopic mixing between the different water masses involved in generating Pacific deep waters lead us to the following conclusions: (1) Small variations in the strength and composition of North Atlantic Deep Water (NADW) have a relatively minor effect on the amounts of lead and neodymium from SCW contributing to the Pacific and (2) an enhanced SCW flow with an open isthmus of Panama, as suggested by General Circulation Models (GCM), requires a corresponding reduction in NADW Pb and Nd contributions to SCW. The general agreement between the isotopic compositions of surface layers of Mn nodules, integrated over such long time intervals, and those of present-day bottom waters at their respective locations show that the present-day ocean circulation pattern has dominated through the Pleistocene. Our study of Mn crust Va13-2 shows that shorter-term changes in lead and neodymium isotope ratios can be resolved, provided that such crusts are sampled at an appropriate time resolution.

Description: Profiles of the 230Th concentration in Mn crusts from the central Pacific Ocean measured at extremely high depth resolution reveal that the growth rates of Mn crusts are influenced by climate. Based on a “constant flux model” the sections of maximum 230Th concentration correspond to periods of slow growth during glacial stages. Fast growth occurred during interglacial stages 1, 5, and 7, probably due to a larger supply of Mn oxides from the water column. High-resolution profiles of 230Th and 10Be in sediment cores from high biological productivity areas display radioisotope maxima in the interglacial stages and minima during glacial periods, the ratio of the fluxes of 10Be/230Th being ≥4. The only exceptions are observed at 135 and 270 kyr B.P., where the ratio of the fluxes is as low as 0.1 to 0.3. We presume that this “230Th anomaly” reflects short periods of time at the end of glacials when precipitation of MnO2 occurred. This hypothesis is confirmed by peaks of Mn observed in sediment cores mainly at the transitions from glacial to interglacial stages. The standing crops of Mn in these layers suggest release of Mn2+ from the sediments during glacial stages and buildup of Mn in the water column to concentrations of up to 10 µmol/L.

Description: Variations of intensity and composition of biogenic particle flux at the northern boundary of the present PolarFrontal Zone in the Atlantic sector of the Southern Ocean are indicators of major changes of paleoenvironmentalconditions on glacial/interglacial time scales during the Late Quaternary. In order to estimate those pastchanges, sediment accumulation patterns of two piston cores, one from just north and one just south of thepresent day position of the Subantarctic Front were reconstructed. Using the 230Thex method large contributionsof laterally supplied material were quantified and used to correct sediment accumulation rates. During the lastglacial focussing of biogenic opal-dominated material exceeded the original contribution from the surfacewater above by a maximum factor of 8.7. The initial activity ratio of 231Paex/230Thex was used as tracer forbiogenic particle flux and composition and indicates that during the glacial stages 2 and 4 the area of high opalproductivity was situated above the location of the southern core whereas the northern core has not beenreached by this northward shift during the last 130 kyr as shown by the pattern of focussing-corrected bulkaccumulation rates. If the position of the Antarctic Polar Front has remained at the northern boundary of thehigh opal productivity area during the last 130 kyr, the results suggest that was located exactly between thetwo core sites during glacial stages 2 and 4. A two-box modeling approach involving particle flux and boundaryscavenging intensity of 231Pa was applied to estimate the possible range of the 231Paex/230Thex ratio recordedin Southern Ocean sediments. Previous estimates on the export of 231Pa from the Atlantic into the SouthernOcean are corroborated but the model suggests a low sensitivity of the 231Paex/230Thex ratio in Southern Oceansediments to variations of the residence time of North Atlantic Deep Water in the Atlantic Ocean.

Description: Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Description: High resolution 230Thex and 10Be and biogenic barium profiles were measured at three sediment gravity cores (length 605–850 cm) from the Weddell Sea continental margin. Applying the 230Thex dating method, average sedimentation rates of 3 cm/kyr for the two cores from the South Orkney Slope and of 2.4 cm/kyr for the core from the eastern Weddell Sea were determined and compared to δ18O and lithostratigraphic results. Strong variations in the radionuclide concentrations in the sediments resembling the glacial/interglacial pattern of the δ18O stratigraphy and the 10Be stratigraphy of high northern latitudes were used for establishing a chronostratigraphy. Biogenic Ba shows a pattern similar to the radionuclide profiles, suggesting that both records were influenced by increased paleoproductivity at the beginning of the interglacials. However, 230Thex0 fluxes (0 stands for initial) exceeding production by up to a factor of 4 suggest that sediment redistribution processes, linked to variations in bottom water current velocity, played the major role in controlling the radionuclide and biogenic barium deposition during isotope stages 5e and 1. The correction for sediment focusing makes the ‘true’ vertical paleoproductivity rates, deduced from the fluxes of proxy tracers like biogenic barium, much lower than previously estimated. Very low 230Thex0 concentrations and fluxes during isotope stage 6 were probably caused by rapid deposition of older, resedimented material, delivered to the Weddell Sea continental slopes by the grounded ice shelves and contemporaneous erosion of particles originating from the water column.

Description: We investigated the influence of the composition of the vertical particle flux on the removal of particle reactive natural radionuclides (Th-230 and Pa-231) from the water column to the sediments. Radionuclide concentrations determined in sediment traps moored in the western, central and eastern Arabian Sea were related to the major components (carbonate, particulate organic matter (POC), opal, lithogenic material) of the particle flux. These data were combined with sediment trap data previously published from the Southern Ocean, Equatorial Pacific and North Atlantic [Z. Chase, R.F. Anderson, M.Q. Fleisher, P.W. Kubik, The influence of particle composition and particle flux on scavenging of Th, Pa and Be in the ocean, Earth Planet. Sci. Lett. 204 (2002) 215-229; J.C. Scholten, F. Fietzke, S. Vogler, M. Rutgers van der Loeff, A. Mangini, W Koeve, J. Waniek. P. Stoffers, A. Antia, J. Kass, Trapping efficiencies of sediment traps from the deep eastern North Atlantic: The Th-230 calibration, Deep Sea Research 1148 (2001) 2383-2408]. The correlations observed between the particle-dissolved distribution coefficients (K-d) of Th-230 and Pa-231 and the concentrations of the particle types depend on the sediment trap data set used. This result suggests that scavenging affinities of the nuclides differ between oceanic regions. Several factors (K-d values, reactive surface areas of particles, inter-correlations in closed data set) can, however, influence the observed relationships and thus hamper the interpretation of these correlation coefficients as a measure of relative scavenging affinities of the nuclides to the particle types investigated. The mean fractionation factor (F(Pa/Th)=K-d(Pa)/(K)d(Th)) from the Equatorial Pacific (F=0.11+/-0.03) is similar to that from the North Atlantic (F(Pa/Th)=0.077+/-0.026), and both are lower than the factors from the Arabian Sea (F(Pa/Th)=0.35+/-0.12) and from the Southern Ocean (F(Pa/Th) 0.87+/-0.4). For opal concentrations exceeding similar to60%, an increase in the fractionation factors is observed causing a higher mean fractionation factor for the Southern Ocean trap data set. For the other areas investigated, differences in the mean fractionation factors cannot be related to the particles types considered. In the Arabian Sea, seasonally variable Pa-231(ex)/Th-230(ex) ratios observed in the sediment traps as well as differences of the ratios between recently deposited phytodetritus (fluff) and normal surface sediments indicate seasonal changes in scavenging processes which the generally accepted reversible scavenging models do not envisage. We assume that variable sinking rates of particles, and/or particles not considered in this study (e.g. colloids, manganese oxides, transparent exopolymer particles) may play an important but as yet unexplored role in deep-water scavenging processes. (C) 2004 Elsevier B.V. All rights reserved.

Description: Marine molluscan shells from para-type and other loclities of the Holsteinian interglaciation were dated by ThU and the electron spin resonance (ESR) method to more than 350,000 and 370,000 yr B.P., beyond the limit of ThU dating. The high age estimate is corroborated by a KAr age of 420,000 yr B.P. determined from volcanic ash near the base of the Ariendorf paleosol in the Middle Rhine valley believed to be a pedostratigraphic equivalent of the Holsteinian. Shells from the Herzeele marine unit III, an equivalent of the Wacken (Dömnitz) warm stage in northern France and subsequent to the Holsteinian, revealed ages between 300,000 and 350,000 yr B.P. A correlation of these two warm stages with marine oxygen-isotope stages 11 and 9 on the SPECMAP and CARTUNE time scales is suggested. From the benthic oxygen-isotope record one may infer that no exceptionally high global sea-level rise corresponds to the large transgressions of the Holstein Sea in northern Germany. Therefore, a significant proportion of the transgression was probably the result of an unusually large local glacial-isostatic depression caused by the extreme buildup of ice during the preceding Elster glaciation (stage 12). According to the deep-sea record, it lasted approximately 50% longer than the subsequent cold stage 10. The outstanding soil formation with Braunlehm and the well-developed thermal optimum of the Holsteinian are tentatively related to a phase of minimum sea-ice cover in the Norwegian-Greenland Sea, as deduced from long benthic carbon-isotope records from the central Atlantic.