Uvigerina spp. d18O and Mg/Ca measurements from sediment cores JR244-GC528 and MD07-3076

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected d18O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer d13C and foraminifer/coral 14C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.

Stable carbon and oxygen isotope record of foraminifera from ODP holes 104-643A and 104-644A

Continuous sediment sections spanning the last 2.8 Ma have been studied using stable isotope stratigraphy and sedimentological methods. By using paleomagnetic reversals as a chronostratigraphic tool, climatic and paleoceanographic changes have been placed in a time framework. The results show that the major expansion of the Scandinavian Ice Sheet to the coastal areas occurred in the late Neogene period at about 2.8 Ma. Relatively high-amplitude glacials appeared until about 2 Ma. The period between 2.8 and 1.2 Ma was marked by cold surface water conditions with only weak influx of temperate Atlantic water as compared with late Quaternary interglacials. During this period, climatic variations were smaller in amplitude than in the late Quaternary. The Norwegian Sea was a sink of deep water throughout the studied period but deep water ventilation was reduced and calcite dissolution was high compared with the Holocene. Deep water formed by other processes than today. Between 2 and 1.2 Ma, glaciations in Scandinavia were relatively small. A transition toward larger glacials took place during the period 1.2 to 0.6 Ma, corresponding with warmer interglacials and increasing influx of temperate surface water during interglacials. A strong thermal gradient was present between the Norwegian Sea and the northeastern Atlantic during the Matuyama (2.5-0.7 Ma). This is interpreted as a sign of a more zonal and less meridional climatic system over the region as compared with the present situation. The transition towards more meridionality took place over several hundred thousand yr. Only during the last 0.6 Ma has the oceanographic and climatic system of the Norwegian Sea varied in the manner described from previous studies of the late Quaternary.

(Table 1) Age determination of North Atlantic sediment cores

High-resolution sediment cores from the Vøring Plateau, the North Iceland shelf, and the East Greenland shelf have been studied to investigate the stability of major surface currents in the Nordic Seas during the Holocene. Results from diatom assemblages and reconstructed sea-surface temperatures (SSTs) indicate a division of the Holocene into three periods: the Holocene Climate Optimum (9500-6500 calendar (cal) years BP), the Holocene Transition Period (6500-3000 cal years BP) and the Cool Late Holocene Period (3000-0 cal years BP). The overall climate development is in step with the decreasing insolation on the Northern Hemisphere, but regional differences occur regarding both timing and magnitude of SST changes. Sites under the direct influence of the Norwegian Atlantic Current and the Irminger Current indicate SST cooling of 4-5°C from early Holocene to present, compared to 2°C recorded under the East Greenland Current. Superimposed on the general Holocene cooling trend, there is a high-frequency SST variability, which is in the order of 1-1.5°C for the Vøring Plateau and the East Greenland shelf and 2.5-3°C on the North Iceland shelf.

(Appendix) Gephyrocapsa coccolith abundance and holocene paleotemperature assessment

A global sea surface temperature calibration based on the relative abundance of different morphotypes within the coccolithophore genus Gephyrocapsa in Holocene deep-sea sediments is presented. There is evidence suggesting that absolute sea surface temperature for a given location can be calculated from the relative abundance of Gephyrocapsa morphotypes in sediment samples, with a standard error comparable to temperature estimates derived from other temperature proxies such as planktic foraminifera transfer functions. A total of 110 Holocene sediment samples were selected from the Pacific, Indian, and Atlantic Oceans covering a mean sea surface temperature gradient from 13.6° to 29.3°C. Standard multiple linear regression analyses were applied to this data set, linking the relative abundance of Gephyrocapsa morphotypes to sea surface temperature. The best model revealed an r**2 of 0.83 with a standard residual error of 1.78°C for the estimation of mean sea surface temperature. This new proxy provides a unique opportunity for the reconstruction of paleotemperatures with a very small amount of sample material due to the minute size of coccoliths, permitting examination of thinly laminated sediments (e.g., a pinhead of material from laminated sediments for the reconstruction of annual sea surface temperature variations). Such fine-scale resolution is currently not possible with any other proxy. Application of this new paleotemperature proxy may allow new paleoenvironmental interpretations in the late Quaternary period and discrepancies between the different currently used paleotemperature proxies might be resolved.

X-ray fluorescent (XRF) ratios and diatom groups of sediment core GeoB13813-4

The continental shelf adjacent to the Río de la Plata (RdlP) exhibits extremely complex hydrographic and ecological characteristics which are of great socioeconomic importance. Since the long-term environmental variations related to the atmospheric (wind fields), hydrologic (freshwater plume), and oceanographic (currents and fronts) regimes are little known, the aim of this study is to reconstruct the changes in the terrigenous input into the inner continental shelf during the late Holocene period (associated with the RdlP sediment discharge) and to unravel the climatic forcing mechanisms behind them. To achieve this, we retrieved a 10 m long sediment core from the RdlP mud depocenter at 57 m water depth (GeoB 13813-4). The radiocarbon age control indicated an extremely high sedimentation rate of 0.8 cm per year, encompassing the past 1200 years (AD 750-2000). We used element ratios (Ti / Ca, Fe / Ca, Ti / Al, Fe / K) as regional proxies for the fluvial input signal and the variations in relative abundance of salinity-indicative diatom groups (freshwater versus marine-brackish) to assess the variability in terrigenous freshwater and sediment discharges. Ti / Ca, Fe / Ca, Ti / Al, Fe / K and the freshwater diatom group showed the lowest values between AD 850 and 1300, while the highest values occurred between AD 1300 and 1850. The variations in the sedimentary record can be attributed to the Medieval Climatic Anomaly (MCA) and the Little Ice Age (LIA), both of which had a significant impact on rainfall and wind patterns over the region. During the MCA, a weakening of the South American summer monsoon system (SAMS) and the South Atlantic Convergence Zone (SACZ), could explain the lowest element ratios (indicative of a lower terrigenous input) and a marine-dominated diatom record, both indicative of a reduced RdlP freshwater plume. In contrast, during the LIA, a strengthening of SAMS and SACZ may have led to an expansion of the RdlP river plume to the far north, as indicated by higher element ratios and a marked freshwater diatom signal. Furthermore, a possible multidecadal oscillation probably associated with Atlantic Multidecadal Oscillation (AMO) since AD 1300 reflects the variability in both the SAMS and SACZ systems.

Organic geochemistry and Rock-Eval pyrolysis at DSDP Leg 79 and 41 Holes

Cenozoic and Mesozoic sediments ranging in age from Pleistocene to Early Jurassic/late Triassic were recovered on DSDP Leg 79, off Morocco at Sites 544 to 547 in front of the Mazagan Plateau. The main zone of oil genesis should be reached at Site 547 within the Jurassic section. Organic material of marine origin with good petroleum potential characterizes the late Eocene slumps of Site 547 and originates from reworked organic matter of Cretaceous origin. Organic enrichment also occurs at Site 545 during the middle to late Albian period. Since the organic matter appears to be autochthonous, reducing environments of deposition are inferred. In the other Cretaceous deposits, variably altered organic matter of the same origin predominates. Finally, a transect including Site 370 off the Agadir Canyon, is studied: detrital organic matter and reducing environments of deposition were more developed during Albian time for Site 370 than for Site 545.

Isotope measurements from late Paleocene - early Eocene of 5 cores from Atlantic and Pacific Ocean

High-resolution stable carbon isotope records for upper Paleocene - lower Eocene sections at Ocean Drilling Program Sites 1051 and 690 and Deep Sea Drilling Project Sites 550 and 577 show numerous rapid (40 - 60 kyr duration) negative excursions of up to 1 per mill. We demonstrate that these transient decreases are the expected result of nonlinear insolation forcing of the carbon cycle in the context of a long carbon residence time. The transients occur at maxima in Earth's orbital eccentricity, which result in high-amplitude variations in insolation due to forcing by climatic precession. The construction of accurate orbital chronologies for geologic sections older than ~ 35 Ma relies on identifying a high-fidelity recorder of variations in Earth's orbital eccentricity. We use the carbon isotope records as such a recorder, establishing a robust orbitally tuned chronology for latest Paleocene-earliest Eocene events. Moreover, the transient decreases provide a means of precise correlation among the four sites that is independent of magnetostratigraphic and biostratigraphic data at the <10^5-year scale. While the eccentricity-controlled transient decreases bear some resemblance to the much larger-amplitude carbon isotope excursion (CIE) that marks the Paleocene/Eocene boundary, the latter event is found to occur near a minimum in the ~400-kyr eccentricity cycle. Thus the CIE occurred during a time of minimal variability in insolation, the dominant mechanism for forcing climate change on 104-year scales. We argue that this is inconsistent with mechanisms that rely on a threshold climate event to trigger the Paleocene/Eocene thermal maximum since any threshold would more likely be crossed during a period of high-amplitude climate variations.

Distribution of benthos in late Quaternary turbidite layers of sediment cores from the North-West African continental margin

The CaCO3-contents and the fractions > 40 µm have been analysed from 5 kastenloten, one piston core and two kastengreifer taken between Senegal and Cape Verde Islands. Numerous benthonic and planktonic organisms and different terrigenous components have been distinguished. The four cores off Senegal reach middle Wuerm sediments; cores GIK12329-6 and TAG72-1 reach the V-zone and core GIK12331-4 the X-zone (Eem); the two kastengreifer contain sediments of Holocene age. Correlation of the cores has been made. Holocene sedimentation rates decrease from the shallow cores (6-11 cm/1000 years) to the deep-sea (1-2 cm/1000 years). The following climatic variations could be deduced from the sediments off the Senegal: during Holocene climate was in general as today, the Senegal river transporting fine grained material to the sea. The upper Wuerm was arid with no river influence but with red dune sand transported to the continental slope. During middle Wuerm the climate was humid again. The deep-sea cores have been influenced by eolian material from arid regions during glacial and interglacial periods, indicated by relatively high "Wuestenquarz-numbers". However, during Wuerm "Wuestenquarz-numbers" are higher than during Holocene and Eem, indicating that more intensely red coloured sediment was exposed to wind activity on the continent during this period. Varying amounts of terrigenous material and CaCO3-contents indicate varying wind strengths (lower in Holocene and Eem than during Wuerm). The boundary between humid and arid Wuerm climate was at approximately 20 °N. Influence of upwelling is difficult to establish in the sediments off Senegal, because river influence, while increasing fertility also dilutes the diatoms which are typical for upwelling. High amounts of organic carbon, low plankton/benthos ratios of foraminifers and low plankton foraminifer/radiolarian ratios in Holocene sections might be interpreted as influenced by upwelling. Turbidites occur in cores 72 and 31 and at the Holocene/Pleistocene boundary of core GIK12329-6. Their composition indicates provenance from the continental shelf of the Cape Verde Islands for core 31 and the continental shelf and slope off Senegal for core TAG72-1. Volcanic material, rare in the normal pelagic sediment of core GIK12331-4 is more frequent in the turbidites.

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Radioisotope stratigraphy, sedimentology and geochemistry of Late Quaternary sediments from the Eastern Arctic Ocean

To reconstruct Recent and past sedimentary environments, marine sediments of Upper Pleistocene and Holocene ages from the eastern Arctic Ocean and especially from the Nansen-Gakkel Ridge (NGR) were investigated by means of radioisotopic, geochemical and sedimentological methods. In combination with mass physical property data and lithological analysis these investigations allow clearly to characterize the depositional environments. Age dating by using the radioisotope 230Th gives evidence that the investigated sediments from the NGR are younger than 250,000 years. Identical lithological sediment sequences within and between sediment cores from the NGR can be related to sedimentary processes which are clearly controlled by palaeoclimate. The sediments consist predominantly of siliciclastic, terrigenous ice-rafted detritus (IRD) deriving from assorted and redeposited sediments from the Siberian shelfs. By their geochemical composition the sediments are similar to mudstone, graywacke and arcose. Sea-ice as well as icebergs play a major roll in marine arctic sedimentation. In the NGR area rapid change in sedimentary conditions can be detected 128,000 years ago. This was due to drastic change in the kind of ice cover, resulting from rapid climatic change within only hundreds of years. So icebergs, deriving mostly from Siberian shelfs, vanished and sea-ice became dominant in the eastern Arctic Ocean. At least three short-period retreats of the shelf ice between 186,000 and 128,000 years are responsible for the change of coarse to fine-grained sediments in the NGR area. These warmer stages lasted between 1,000 and 3,000 years. By monitoring and comparing the distribution patterns of sedimentologic, mass physical and geochemical properties with 230Th ex activity distribution patterns in the sediment cores from the NGR, there is clear evidence that sediment dilution is responsible for high 230Th ex activity variations. Thus sedimentation rate is the controlling factor of 230Th ex activity variations. The 230Th flux density in sediments from the NGR seems to be highly dependent On topographic Position. The distribution patterns of chemical elements in sediment cores are in general governed by lithology. The derivation of a method for dry bulk density determination gave the opportunity to establish a high resolution stratigraphy on sediment cores from the eastern Arctic Ocean, based on 230Thex activity analyses. For the first time sedimentation and accumulation rates were determined for recent sediments in the eastern Arctic Ocean by 230Th ex analyses. Bulk accumulation rates are highly variable in space and time, ranging between 0.2 and 30 g/cm**2/ka. In the sediments from the NGR highly variable accumulation rates are related to the kind of ice cover. There is evidence for hydrothermal input into the sediments of the NGR. Hydrothermal activity probably also influences surficial sediments in the Sofia Basin. High contents of As are typical for surficial sediments from the NGR. In particular SL 370-20 from the bottom of the rift valley has As contents exceeding in parts 300 ppm. Hydrothermal activity can be traced back to at least 130,000 years. Recent to subrecent tectonic activity is documented by the rock debris in KAL 370 from the NGR. In four other sediment cores from the NGR rift valley area tectonically induced movements can be dated to about 130,000 years ago, related most probably to the rapid climate change. Processes of early diagenesis in sediments from the NGR caused the aobilization and redeposition of Fe, Mn and Mo. These diagenetic processes probably took place during the last 130,000 years. In sediment cores from the NGR high amounts of kaolinite are related to coarse grained siliciclastic material, probably indicating reworking and redeposition of siberian sandstones with kaolinitic binding material. In contrast to kaolinite, illite is correlated to total clay and 232Th contents. Aragonite, associated with serpentinites in the rift valley area of the NGR, was precipitated under cold bottom-water conditions. Preliminary data result in a time of formation about 60 - 80 ka ago. Manganese precipitates with high Ni contents, which can be related to the ultrabasic rocks, are of similar age.

Sedimentology and geochemistry of late glacial and Holocene sediments from Laguna Potrok Aike, Patagonia

A high-resolution multiproxy geochemical approach was applied to the sediments of Laguna Potrok Aike in an attempt to reconstruct moist and dry periods during the past 16 000 years in southeastern Patagonia. The age-depth model is inferred from AMS 14C dates and tephrochronology, and suggests moist conditions during the Lateglacial and early Holocene (16 000-8700 cal. BP) interrupted by drier conditions before the beginning of the Holocene (13 200-11 400 cal. BP). Data also imply that this period was a major warm phase in southeastern Patagonia and was approximately contemporaneous with the Younger Dryas chronozone in the Northern Hemisphere (12 700-11 500 cal. BP). After 8650 cal. BP a major drought may have caused the lowest lake level of the record. Since 7300 cal. BP, the lake level rose and was variable until the 'Little Ice Age', which was the dominant humid period after 8650 cal. BP.

Late Pliocene stratigraphic distribution of Globoconella taxa in the North Atlantic

Quantitative records of Globorotalia puncticulata and Globorotalia inflata, the last two members of the Globorotalia (Globoconella) lineage, obtained from North Atlantic sediments collected at DSDP Site 552, ODP Site 659 and ODP Site 665, are used to examine fluctuations in the biogeographic distribution of these species in the Late Pliocene between 3 and 2 Ma. Abundance data indicate that prior to the expansion of Northern Hemisphere glaciation at about 2.5 Ma, Gr. puncticulata was an important component of the planktonic foraminiferal fauna and had a geographic distribution ranging from 2°N to at least 56°N in the North Atlantic. A previously undescribed 6 chambered variant of Gr. puncticulata is found at both Sites 659 and 665. The stratigraphic distribution of this morphotype is restricted, first occurring at 2.9 Ma and then disappearing when glacial intensity increased at 2.75 Ma (isotope stage 110). Similar declines in Gr. puncticulata abundances occurred during glacial isotope stages 102, 100, and 98 immediately prior to the extinction of Gr. puncticulata during glacial isotope stage 96. It appears that this extinction event was latitudinally diachronous within the North Atlantic, occurring earliest in the north at Site 552 (2.453 Ma), then at Site 659 (2.443 Ma) and later still in the Site 665 equatorial record (2.438 Ma). At Site 665 the first record of Gr. inflata occurs during glacial isotope stage 94 (2.416 Ma), shortly after the extinction of Gr. puncticulata. In the mid latitude North Atlantic there was a 340,000 year period following the disappearance of Gr. puncticulata when the Globoconella lineage was absent (the Gr. inflata gap). The Gr. inflata population found in the equatorial Atlantic must therefore have been introduced from the South Atlantic, probably by the South Equatorial Current. Faunal records from Sites 552 and 659 show that it was not until glacial isotope stage 78 (2.10 Ma) that Gr. inflata became widely established in the North Atlantic. Prior to this large-scale migration event, there were two limited colonisation events during glacial isotope stages 86 and 82 when Gr. inflata populations reached as far as Site 659 in the eastern North Atlantic. These incursions are believed to be reflect the entrainment of Gr. inflata within South Atlantic Central Water and the northward subsurface transport of individuals to the coastal upwelling zone off northwest Africa. It seems likely that the same mechanism was responsible for the re-establishment of the Globoconella lineage in the North Atlantic at 2.10 Ma, but in this instance additional factors, such as enhanced glacial circulation patterns and ecological changes within planktonic foraminiferal faunas, resulted in the successful expansion of Gr. inflata across the North Atlantic and the Mediterranean.

Size-related stable isotope changes in Late Cretaceous and Recent planktic foraminifera from the western tropical Atlantic

The paleoecology of Cretaceous planktic foraminifera during the Late Cenomanian to Coniacian period (~95-86 Ma) remains controversial since much of the tropical marine record is preserved as chalk and limestone with uncertain geochemical overprints. Here we present delta13C and delta18O data from sieve size fractions of monospecific samples of exceptionally well preserved planktic foraminifera recovered during Ocean Drilling Program Leg 207 (Demerara Rise, western tropical Atlantic). Our results suggest that all species studied (Hedbergella delrioensis, Heterohelix globulosa, Marginotruncana sinuosa, Whiteinella baltica) grew primarily in surface waters and did not change their depth habitat substantially during their life cycle. Comparison of size-related ontogenetic trends in delta13C in Cretaceous and modern foraminifera further suggests that detection of dinoflagellate photosymbiosis using delta13C is confounded by physiological effects during the early stages of foraminifer growth, raising doubts about previous interpretations of photosymbiosis in small foraminifera species. We propose that obligate photosymbiosis involving dinoflagellates may not have evolved until the Campanian or Maastrichtian since our survey of Cenomanian-Coniacian species does not find the delta18O and delta13C size-related trends observed in modern foraminifer-dinoflagellate symbioses.