Geochemistry of Eocene/Oligocene sediments of ODP Hole 154-925A

Paleoproductivity, nutrient burial, and carbon cycling were investigated across the Eocene/Oligocene (E/O) boundary (begin to end; 36.9-32.7 Ma at ~40 kyr resolution, timescale of Shackleton et al. (1999, doi:10.1098/rsta.1999.0407) at Ocean Drilling Program Site 925 on the Ceara Rise in the western equatorial Atlantic (3040 m present water depth; 748.26-850.70 mbsf). Downcore bulk sediment records of biogenic barium, total reactive phosphorus, biogenic silica, and calcium carbonate are interpreted to represent export production, net nutrient burial, biogenic opal production, and inorganic carbon burial, respectively. The global positive excursion in d13C subsequent to the E/O boundary is recorded at Site 925. Export production appears to have been externally forced by orbital parameters at eccentricity frequencies during the study interval, based on spectral analysis of the biogenic barium and reactive phosphorus records. Biogenic silica production or preservation increased after the Eocene/Oligocene boundary to a higher baseline, although overall productivity and nutrient burial did not increase, based on barium and reactive phosphorus records. Thus, although absolute production did not increase at this site, a shift in relative abundance of siliceous versus carbonate productivity may have resulted in a change in relative organic carbon burial. This may have contributed to the positive excursion in global oceanic d13C subsequent to the Eocene/Oligocene boundary, although the silica maximum persists after the carbon isotope excursion ends.

Age determination of sediment cores of the southeastern Weddell Sea, Antarctica

On the continental margin of the southeastern Weddell Sea, Antarctica, several channel-ridge systems can be traced on the eastern side of the Crary Fan. Swath mapping of the bathymetry reveals three southwest-northeast trending ridges up to 300 m high with channels on their southeastern side. The structures occur on a terrace of the continental slope in water depths of 2000 - 3300 m. We carried out sedimentological studies on cores from three sites. Two of the studied cores are from ridges, one is from the northwestern part of the terrace. The stratigraphy of the recovered sediments is based on accelerator mass spectrometer 14C determinations, stable oxygen and carbon isotopes analyses and paleomagnetic measurements. The sediments represent a period from the last glacial maximum (LGM) to recent time. They are composed predominantly of terrigenous components. We distinguish four different sedimentary facies and assign them to processes controlling sedimentation. Microlaminated muds and cross-stratified coarse-silty sediments originated from contour currents. Bioturbated sediments reflect the increasing influence of hemipelagic sedimentation. Structureless sediments with high contents of ice-rafted debris characterize slumps. The inferred contour currents shaping the continental slope during the LGM were canalized within the channels and supplied microlaminated mud to the western sedimentary ridges due to deflection to the left induced by the Coriolis force. The lamination of the sediments is attributed to seasonal variations of current velocities. The thermohaline bottom currents were directed to the northeast and hence opposite to the Weddell Gyre. Cross-stratified coarse-silty contourites on the ridges are intercalated with the muds and indicate spillover of faster thermohaline flows. Average sedimentation rates on the terrace of the continental slope were unusually high (250 cm/ka) during the LGM, indicating active growth phases of the Crary Fan during glacial intervals. A substantial environmental change at 19.5 - 20 ka is documented in the sediments by a gradual change from lamination to bioturbation. During the recent interglacial, bioturbated sediments were deposited in all parts of the terrace. Because of a reduction of the contour current velocities (4-7 cm/s), the water masses of the Weddell Gyre, supplying fine-grained sediments from northeast, gain a greater influence on sedimentation on the continental slope. Higher percentages of microfossils indicate enhanced biogenic productivity. Increased iceberg activity is documented by greater amounts of ice-rafted debris. The interglacial sedimentation rates decrease to a few cm/ka and indicate that the Crary Fan became relatively sediment-starved during interglacial intervals.

(Table 2) Uranium and thorium isotopic composition, activity ratios and ages of bivalvia shells in sediment core GIK14350, northern Germany

A new chemical procedure for cleaning marine carbonates was applied to remove detritus as well as metaloxide contaminations of marine shells from Eemian deposits and adjoining succession of a sediment core from Dagebüll, Schleswig- Holstein. Hence, one can significantly reduce the contamination with detrital uranium and thorium. Thermal ionisation mass spectrometry was applied to determine the uranium and thorium activities used for 230Th/U dating of these shells. At least ten samples of marine bivalves of five different core sections were analysed. Samples located below a five meter thick clay layer at 19-24 m yielded an average age of 132±18 ka. Shells located above the clays at 15-20 m depth were strongly influenced by percolating groundwaters of an open system. Therefore, a reliable dating of these samples was not possible.

Geochemistry of Apatite from rapid cooled samples

Apatite (U-Th-Sm)/He (AHe) thermochronology is increasingly used for reconstructing geodynamic processes of the upper crust and the surface. Results of AHe thermochronology, however, are often in conflict with apatite fission track (AFT) thermochronology, yielding an inverted age-relationship with AHe dates older than AFT dates of the same samples. This effect is mainly explained by radiation damage of apatite, either impeding He diffusion or causing non-thermal annealing of fission tracks. So far, systematic age inversions have only been described for old and slowly cooled terranes, whereas for young and rapidly cooled samples 'too old' AHe dates are usually explained by the presence of undetected U and/or Th-rich micro-inclusions. We report apatite (U-Th-Sm)/He results for rapidly cooled volcanogenic samples deposited in a deep ocean environment with a relatively simple post-depositional thermal history. Robust age constraints are provided independently through sample biostratigraphy. All studied apatites have low U contents (< 5 ppm on average). While AFT dates are largely in agreement with deposition ages, most AHe dates are too old. For leg 43, where deposition age of sampled sediment is 26.5-29.5 Ma, alpha-corrected average AHe dates are up to 45 Ma, indicating overestimations of AHe dates up to 50%. This is explained by He implantation from surrounding host U-Th rich sedimentary components and it is shown that AHe dates can be "corrected" by mechanically abrading the outer part of grains. We recommend that particularly for low U-Th-apatites the possibility of He implantation should be carefully checked before considering the degree to which the alpha-ejection correction should be applied.

Fine-silt luminescence dating and mineral composition of sediments from the Arctic Ocean

New geochronometers are needed for sediments of the Arctic Ocean spanning at least the last half million years, largely because oxygen-isotope stratigraphy is relatively ineffective in this ocean, and because other dating techniques require significant assumptions about sedimentation rates. Multi-aliquot luminescence sediment-dating procedures were applied to polymineral, fine-silt samples from 9 core-top and 37 deeper samples from 20 cores representing 19 sites across the Arctic Ocean. Most samples have independent age assignments and other known properties (e.g., % coarse fraction, % carbonate, U-Th isotopes). Thick-source alpha-particle counting indicates that for most regions the contribution of measured unsupported 230Th and 231Pa to calculated dose rates is

Age and isotopes in bottom sediments from Core VER-99-1-St2, Baikal Lake

A simple, reliable, and efficient method has been elaborated for direct determination of isotopic composition of authigenic uranium in siliceous lacustrine sediments. The method is based on studying kinetics of selective extraction of authigenic uranium from sediments by weak solutions of ammonium hydrocarbonate followed by ICP-MS analysis of nuclides. To estimate contamination of authigenic uranium by terrigenous one contents of 232Th and some other clastogenic elements in the extracts were measured simultaneously. Selectivity of extraction of authigenic uranium from the sediments treated with 1% NH4HCO3 solution appeared to be no worse than 99%. The method was applied to analysis of isotopic composition of authigenic uranium at several key horizons of the earlier dated core from the Baikal Lake. Measurements directly show that 234U/238U values in Baikal water varied depending on climate, which contradicts existing hypotheses. Measured 234U/238U ratios in water of the paleo-Baikal match corresponding values reconstructed from isotopic data for total uranium in the sediments on supposition that U/Th ratio is constant in terrigenous fraction of the sediments. Direct experimental determination of total and authigenic nuclides in sediments enhances potentiality of the method for 234U-230Th dating of non-carbonate lacustrine sediments including those from the Baikal Lake within intervals corresponding to periods of glaciation, when sediments were rich in terrigenous components. Portions of terrigenous and authigenic uranium are well separated and we can study variability of sources of terrigenous matter and refine the earlier model for reconstructing climate humidity in the East Siberia.

Lithostratigraphy determined from downhole logs in the AND-2A borehole

During the 2007-2008 austral spring season, the ANDRILL (Antarctic Drilling project) Southern McMurdo Sound Project recovered an 1138-m-long core, representing the last 20 m.y. of glacial history. An extensive downhole logging program was successfully carried out. Due to drill hole conditions, logs were collected in several passes from the total depth at 1138.54 m below seafloor (mbsf) to 230 mbsf. After data correction, several statistical methods, such as factor analysis, cluster analysis, box-and-whisker diagrams, and cross-plots, were applied. The aim of these analyses was to use detailed interpretation of the downhole logs to obtain a description of the lithologies and their specific physical properties that is independent of the core descriptions. The sediments were grouped into the three main facies, diamictite, mudstone and/or siltstone, and sandstone, and the physical properties of each were determined. Notable findings include the high natural radioactivity values in sandstone and the high and low magnetic susceptibility values in mudstone and/or siltstone and in sandstone. A modified lithology cluster column was produced on the basis of the downhole logs and statistical analyses. It was possible to use the uranium content in the downhole logs to determine hiatuses and thus more accurately place the estimated hiatuses. Using analyses from current literature (geochemistry, clasts, and clay minerals) in combination with the downhole logs (cluster analysis), the depths 225 mbsf, 650 mbsf, 775 mbsf, and 900 mbsf were identified as boundaries of change in sediment composition, provenance, and/or environmental conditions. The main use of log interpretation is the exact definition of lithological boundaries and the modification of the paleoenvironmental interpretation.

(Table 1) Details on the Uranium/Thorium age determinations carried out on core GeoB11569-2

Cold-water corals are widely distributed along the Atlantic continental margin with varying growth patterns in relation to their specific environment. Here, we investigate the long-term development of cold-water corals that once thrived on a low-latitude (17°40'N) cold-water coral mound in the Banda Mound Province off Mauritania during the last glacial-interglacial cycle. U/Th dates obtained from 20 specimens of the cold-water coral Lophelia pertusa, revealed three distinct periods of coral growth during the last glacial at 65 to 57 kyr BP, 45 to 32 kyr BP and 14 kyr BP, thus comprising the cool periods of Marine Isotopic Stages (MIS) 2-4. These coral growth periods occur during periods of increased productivity in the region, emphasizing that productivity seems to be the major steering factor for coral growth off Mauritania, which is one of the major upwelling regions in the world. This pattern differs from the well studied coral mounds off Ireland, where the current regime predominantly influences the prosperity of the cold-water corals. Moreover, coral growth off Ireland takes place during rather warm interglacial and interstadial periods, whereas off Mauritania coral growth is restricted to glacial and stadial periods. However, the on-mound sedimentation patterns off Mauritania largely resemble the observations reported from the Irish mounds. The bulk of the preserved sediments derives from periods of coral growth, whereas during periods without corals hardly any net sedimentation or mound growth took place.

Composition of noble gases in sediments and metasediments

Solar-type helium (He) and neon (Ne) in the Earth's mantle were suggested to be the result of solarwind loaded extraterrestrial dust that accumulated in deep-sea sediments and was subducted into the Earth's mantle. To obtain additional constraints on this hypothesis, we analysed He, Ne and argon (Ar) in high pressure-low temperature metamorphic rocks representing equivalents of former pelagic clays and cherts from Andros (Cyclades, Greece) and Laytonville (California, USA). While the metasediments contain significant amounts of 4He, 21Ne and 40Ar due to U, Th and K decay, no solar-type primordial noble gases were observed. Most of these were obviously lost during metamorphism preceding 30 km subduction depth. We also analysed magnetic fines from two Pacific ODP drillcore samples, which contain solar-type He and Ne dominated by solar energetic particles (SEP). The existing noble gas isotope data of deep-sea floor magnetic fines and interplanetary dust particles demonstrate that a considerable fraction of the extraterrestrial dust reaching the Earth has lost solar wind (SW) ions implanted at low energies, leading to a preferential occurrence of deeply implanted SEP He and Ne, fractionated He/Ne ratios and measurable traces of spallogenic isotopes. This effect is most probably caused by larger particles, as these suffer more severe atmospheric entry heating and surface ablation. Only sufficiently fine-grained dust may retain the original unfractionated solar composition that is characteristic for the Earth's mantle He and Ne. Hence, in addition to the problem of metamorphic loss of solar noble gases during subduction, the isotopic and elemental fractionation during atmospheric entry heating is a further restriction for possible subduction hypotheses.

Stable isotope, UK'37, SST, chlorin, alkenone and TOC data of sediment cores GIK17927-2 and GIK17928-3

Upwelling intensity in the South China Sea has changed over glacial-interglacial cycles in response to orbital-scale changes in the East Asian Monsoon. Here, we evaluate new multi-proxy records of two sediment cores from the north-eastern South China Sea to uncover millennial-scale changes in winter monsoondriven upwelling over glacial Terminations I and II. On the basis of U/Th-based speleothem chronology, we compare these changes with sediment records of summer monsoondriven upwelling east of South Vietnam. Ocean upwelling is traced by reduced (UK'37-based) temperature and increased nutrient and productivity estimates of sea surface water (d13C on planktic foraminifera, accumulation rates of alkenones, chlorins, and total organic carbon). Accordingly, strong winter upwelling occurred north-west of Luzon (Philippines) during late Marine Isotope Stage 6.2, Heinrich (HS) and Greenland stadials (GS) HS-11, GS-26, GS-25, HS-1, and the Younger Dryas. During these stadials, summer upwelling decreased off South Vietnam and sea surface salinity reached a maximum suggesting a drop in monsoon rains, concurrent with speleothem records of aridity in China. In harmony with a stadial-to-interstadial see-saw pattern, winter upwelling off Luzon in turn was weak during interstadials, in particular those of glacial Terminations I and II, when summer upwelling culminated east of South Vietnam. Most likely, this upwelling terminated widespread deep-water stratification, coeval with the deglacial rise in atmospheric CO2. Yet, a synchronous maximum in precipitation fostered estuarine overturning circulation in the South China Sea, in particular as long as the Borneo Strait was closed when sea level dropped below -40 m.

Isotope analysis and heat flow measurements of Maria S. Merian cruise MSM21/4 on the western Svalbard margin

Methane hydrate is an ice-like substance that is stable at high-pressure and low temperature in continental margin sediments. Since the discovery of a large number of gas flares at the landward termination of the gas hydrate stability zone off Svalbard, there has been concern that warming bottom waters have started to dissociate large amounts of gas hydrate and that the resulting methane release may possibly accelerate global warming. Here, we can corroborate that hydrates play a role in the observed seepage of gas, but we present evidence that seepage off Svalbard has been ongoing for at least three thousand years and that seasonal fluctuations of 1-2°C in the bottom-water temperature cause periodic gas hydrate formation and dissociation, which focus seepage at the observed sites.

Tab. I: Alkenon analyses on sample material of cores Krummland KR-1 und Dagebüll DA-1

Geochemical studies of organic "biomarker" compounds were applied to Eemian sediments cored at Dagebuell (DA-1) on the west coast, and at Krummland (KR-1) in the east of the Baltic Zone of Schleswig-Holstein, Germany. 10 samples from the early stage of the Eemian Transgression to the high Eem at Krummland, and 24 samples from the peak and late phases of the Eemian at Dagebuell provide new insights on the development of the Eemian Sea in the region. C37-C39-ethyl- and methyl-ketones in the Krummland sediments indicated unstable conditions at the onset of the marine trangression, and freshwater influence in keeping with their shallow nearshore environment. In the Dagebuell deposits, patterns typical of marine to brackish conditions were observed, comparable to those found today in the Skagerrak and Belt Sea areas. The sea-surface temperatures estimated from the alkenone unsaturation ratio UK37 at DA-1 corroborate the evidence from "standard" faunal and pollen assemblages, and lithological successions. Here, the temperature maximum attained in pollen assemblage zone PAZ Illc, indicates the early onset of very warm conditions, preceding the highest sea level of the penultimate interglacial by 8,000 years, based on previously published U/Th ages.