Late Eocene to early Oligocene carbonate and barite accumulation rates in the Pacific Basin

The late Eocene through earliest Oligocene (40-32 Ma) spans a major transition from greenhouse to icehouse climate, with net cooling and expansion of Antarctic glaciation shortly after the Eocene/Oligocene (E/O) boundary. We investigated the response of the oceanic biosphere to these changes by reconstructing barite and CaCO3 accumulation rates in sediments from the equatorial and North Pacific Ocean. These data allow us to evaluate temporal and geographical variability in export production and CaCO3 preservation. Barite accumulation rates were on average higher in the warmer late Eocene than in the colder early Oligocene, but cool periods within the Eocene were characterized by peaks in both barite and CaCO3 accumulation in the equatorial region. We infer that climatic changes not only affected deep ocean ventilation and chemistry, but also had profound effects on surface water characteristics influencing export productivity. The ratio of CaCO3 to barite accumulation rates, representing the ratio of particulate inorganic C accumulation to Corg export, increased dramatically at the E/O boundary. This suggests that long-term drawdown of atmospheric CO2 due to organic carbon deposition to the seafloor decreased, potentially offsetting decreasing pCO2 levels and associated cooling. The relatively larger increase in CaCO3 accumulation compared to export production at the E/O suggests that the permanent deepening of the calcite compensation depth (CCD) at that time stems primarily from changes in deep water chemistry and not from increased carbonate production.

Composition of Aleutian forearc sediments

The ultimate composition of any sandstone is affected by a host of primary and secondary factors, including the lithologies present in source terranes, climate, depositional environment and diagenesis. In the case of a subduction complex, however, unequivocal identification of detrital provenance may be impossible because of the cumulative effects of tectonic and sedimentary transport. Long-distance sedimentary transport (> 1000 km) is common within trenches, and abyssal-plain turbidites can be tectonically transported for long distances as the underlying oceanic basement drifts towards a subduction front. Post-accretionary displacement can occur as a consequence of strike-slip faulting, and the total distance of tectonic dislocation may reach several thousand kilometers. The present-day Aleutian forearc region (North Pacific Ocean) illustrates many of the "problems" which typify subduction zones. Several petrologic suites can be identified, and there are significant variations in detrital modes in both time and space. The Aleutian region serves as a sobering modern analog for accreted rock units such as the Franciscan Complex of California, where intercalations of discrete sandstone suites have been noted. In the absence of paleomagnetic control, interpretations of sediment provenance within ancient subduction complexes probably should be restricted to the generic level.

Sedimentological, mineralogical, biogeochemical and micropaleontological parameters on sediment core PS69/849-2, Burton Basin, MacRobertson Shelf, East Antarctica

A multi-proxy study including sedimentological, mineralogical, biogeochemical and micropaleontological methods was conducted on sediment core PS69/849-2 retrieved from Burton Basin, MacRobertson Shelf, East Antarctica. The goal of this study was to depict the deglacial and Holocene environmental history of the MacRobertson Land-Prydz Bay region. A special focus was put on the timing of ice-sheet retreat and the variability of bottom-water formation due to sea ice formation through the Holocene. Results from site PS69/849-2 provide the first paleo-environmental record of Holocene variations in bottom-water production probably associated to the Cape Darnley polynya, which is the second largest polynya in the Antarctic. Methods included end-member modeling of laser-derived high-resolution grain size data to reconstruct the depositional regimes and bottom-water activity. The provenance of current-derived and ice-transported material was reconstructed using clay-mineral and heavy-mineral analysis. Conclusions on biogenic production were drawn by determination of biogenic opal and total organic carbon. It was found that the ice shelf front started to retreat from the site around 12.8 ka BP. This coincides with results from other records in Prydz Bay and suggests warming during the early Holocene optimum next to global sea level rise as the main trigger. Ice-rafted debris was then supplied to the site until 5.5 cal. ka BP, when Holocene global sea level rise stabilized and glacial isostatic rebound on MacRobertson Land commenced. Throughout the Holocene, three episodes of enhanced bottom-water activity probably due to elevated brine rejection in Cape Darnley polynya occured between 11.5 and 9 cal. ka BP, 5.6 and 4.5 cal. ka BP and since 1.5 cal. ka BP. These periods are related to shifts from warmer to cooler conditions at the end of Holocene warm periods, in particular the early Holocene optimum, the mid-Holocene warm period and at the beginning of the neoglacial. In contrast, between 7.7 and 6.7 cal. ka BP, brine rejection shut down, maybe owed to warm conditions and pronounced open-water intervals.

Grain size and description on gravity core samples from ANT-IV/2 expedition to the Bransfield Strait

From the above and the grafical results it can be concluded that cores in the research area are locally dominated by turbiditic sequences, which can be observed by a strong increase in coarser sediment (>35 µm). These coarser intercalations are lacking in the vicinity of basaltic seamounts, probably due to a shadowing effect of the seamounts. The infill of the King George Basin might be dominated by a north eastern current. Sedimentary structures as observed in the cores are often lacking or vague due to hydrothermal effects (Suess, L, 1986).

Isotope compositions and mineralogy of carbonates and barites from sediments of the Deryugin Basin (Sea of Okhotsk)

Results of studies of mineralogy, geochemistry, and isotope parameters (d13C, d34S, d180, and 87Sr/86Sr) of carbonates and barites from sediments of the Deryugin Basin in the Sea of Okhotsk are presented. Diagenetic nature of carbonates and barites formed due to prolonged activity of cold seeps acting along a fracture zone and supplying methane- and barium saturated fluids is determined. Any signs for hydrothermal activity were not observed.

Chemistry of Late Quaternary sediments and their interstitial waters of sediment cores from the Nort-West African continental margin

In the sediments of the NW African continental margin the mainly biogenic carbonate constituents become increasingly diluted with terrigenous material as one approaches the coast, as indicated by the carbonate-CO2 content, the Al2O3/SiO2-ratios, and the presence of ammonia fixed to alumino-silicates, predominantly to illites. In the norther area of the investigation - off Cape Blanc and Cape Bojador . the terrigenous constituents are mainly quartz from the Sahara Desert, whereas in the south - off Senegal - more alumino-silicates as clay minerals are admixed with the carbonate constituents. The organic carbon content of the continental slope sediments off Senegal is higher than in samples of the continental rise or of the preservation of organic matter as a result of high production and relatively rapid sedimentation. The zone of manganese-oxide enrichment follows the redox potential of + 330 mV from the surface (0-5 cm) into the sediments (20-30 cm deep) at 2000--3000 m and 3700 m of water depths, respectively. At shallower water depths, low redox potentials preclude deposition of manganese oxides and cause their mobilization from the sediments. About 1/3 of the total sedimentary Zn and 1/4 of the Cu is associated with the carbonate mineral fraction, probably in calcium phosphate overgrowths as a result of the mineralization of phosphorus-containing organic matter. Besides the precipitation of calcium phosphate, the mineralization of organic matter mediated by bacterial sulfate reduction also results in calcium carbonate precipitation and the exchange of ammonia for potassium on illites. Because of these simultaneous reactions, the depth distribution of all mineralization constituents in the interstitial water can be determined using the actual molar carbon-to-nitrogen-to phosphorus ratios of the sedimentary organic matter. The amount of sulfide sulfur in this process indicates the predominance of bacterial sulfate reduction in the sediments off NW Africa. This process also preferentially decomposes nitrogen- and phosphorus-containing organic compounds so organic matter deficient in these elements is characteristic for the rapidly accumulating sediments than today, indicating there was increased production of organic carbon compounds and more favorable conditions of their preservations. During the last interglacial times conditions were similar to those to today. This differentiation with time has also been observed in sediments from the Argentine Basin and from slope off South India indicating perhaps world-wide environmental changes throughout Late Quaternary times.

(Table 2) Age determination of sediment cores from the Panama Basin

Application of the 230Th normalization method to estimate sediment burial fluxes in six cores from the eastern equatorial Pacific (EEP) reveals that bulk sediment and organic carbon fluxes display a coherent regional pattern during the Holocene that is consistent with modern oceanographic conditions, in contrast with estimates of bulk mass accumulation rates (MARs) derived from core chronologies. Two nearby sites (less than 10 km apart), which have different MARs, show nearly identical 230Th-normalized bulk fluxes. Focusing factors derived from the 230Th data at the foot of the Carnegie Ridge in the Panama Basin are >2 in the Holocene, implying that lateral sediment addition is significant in this part of the basin. New geochemical data and existing literature provide evidence for a hydrothermal source of sediment in the southern part of the Panama Basin and for downslope transport from the top of the Carnegie Ridge. The compilation of core records suggests that sediment focusing is spatially and temporally variable in the EEP. During oxygen isotope stage 2 (OIS 2, from 13-27 ka BP), focusing appears even higher compared to the Holocene at most sites, similar to earlier findings in the eastern and central equatorial Pacific. The magnitude of the glacial increase in focusing factors, however, is strongly dependent on the accuracy of age models. We offer two possible explanations for the increase in glacial focusing compared to the Holocene. The first one is that the apparent increase in lateral sediment redistribution is partly or even largely an artifact of insufficient age control in the EEP, while the second explanation, which assumes that the observed increase is real, involves enhanced deep sea tidal current flow during periods of low sea level stand.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Alkenones and SST of surface sediments (Appendix)

We have analysed alkenones in 149 surface sediments from the eastern South Atlantic in order to establish a sediment-based calibration of the U37K' paleotemperature index. Our study covers the major tropical to subpolar production systems and sea-surface temperatures (SST's) between 0° and 27°C. In order to define the most suitable calibration for this region, the U37K' values were correlated to seasonal, annual, and production-weighted annual mean atlas temperatures and compared to previously published culture and core-top calibrations. The best linear correlation between U37K' and SST was obtained using annual mean SST from 0 to 10 m water depth (U37K' = 0.033 T + 0.069, r**2 = 0.981). Data scattering increased significantly using temperatures of waters deeper than 20 m, suggesting that U37K' reflects mixed-layer SST and that alkenone production at thermocline depths was not high enough to significantly bias the mixed-layer signal. Regressions based on both production-weighted and on actual annual mean atlas SST were virtually identical, indicating that regional variations in the seasonality of primary production have no discernible effect on the U37K' vs. SST relationship. Comparison with published core-top calibrations from other oceanic regions revealed a high degree of accordance. We, therefore, established a global core-top calibration using U37K' data from 370 sites between 60°S and 60°N in the Atlantic, Indian, and Pacific Oceans and annual mean atlas SST (0-29°C) from 0 m water depth. The resulting relationship (U37K' = 0.033 T + 0.044, r**2 = 958) is identical within error limits to the widely used E. huxleyi calibrations of and attesting their general applicability. The observation that core-top calibrations extending over various biogeographical coccolithophorid zones are strongly linear and in better accordance than culture calibrations suggests that U37K' is less species-dependent than is indicated by culture experiments. The results also suggest that variations in growth rate of algae and nutrient availability do not significantly affect the sedimentary record of U37K' in open ocean environments.

Pleistocene rhyolithic tephra of ODP Leg 181 sites

Taupo Volcanic Zone (TVZ), in the North Island, New Zealand, is arguably the most active Quaternary rhyolitic system in the world. Numerous and widespread rhyolitic tephra layers, sourced from the TVZ, form valuable chronostratigraphic markers in onshore and offshore sedimentary sequences. In deep-sea cores from Ocean Drilling Program (ODP) Leg 181 Sites 1125, 1124, 1123 and 1122, located east of New Zealand, ca 100 tephra beds are recognised post-dating the Plio-Pleistocene boundary at 1.81 Ma. These tephras have been dated by a combination of magnetostratigraphy, orbitally tuned stable-isotope data and isothermal plateau fission track ages. The widespread occurrence of ash offshore to the east of New Zealand is favoured by the small size of New Zealand, the explosivity of the mainly plinian and ignimbritic eruptions and the prevailing westerly wind field. Although some tephras can be directly attributed to known TVZ eruptions, there are many more tephras represented within ODP-cores that have yet to be recognised in near-source on-land sequences. This is due to proximal source area erosion and/or deep burial as well as the adverse effect of vapour phase alteration and devitrification within near-source welded ignimbrites. Despite these difficulties, a number of key deep-sea tephras can be reliably correlated to equivalent-aged tephra exposed in uplifted marine back-arc successions of Wanganui Basin where an excellent chronology has been developed based on magnetostratigraphy, orbitally calibrated sedimentary cycles and isothermal plateau fission track ages on tephra. Significant Pleistocene tephra markers include: the Kawakawa, Omataroa, Rangitawa/Onepuhi, Kaukatea, Kidnappers-B, Potaka, Unit D/Ahuroa, Ongatiti, Rewa, Sub-Rewa, Pakihikura, Ototoka and Table Flat Tephras. Six other tephra layers are correlated between ODP-core sites but have yet to be recognised within onshore records. The identification of Pleistocene TVZ-sourced tephras within the ODP record, and their correlation to Wanganui Basin and other onshore sites is a significant advance as it provides: (1) an even more detailed history of the TVZ than can be currently achieved from the near-source record, (2) a high-resolution tephrochronologic framework for future onshore-offshore paleoenvironmental reconstructions, and (3) well-dated tephra beds correlated from the offshore ODP sites with astronomically tuned timescales provide an opportunity to critically evaluate the chronostratigraphic framework for onshore Plio-Pleistocene sedimentary sequences (e.g. Wanganui Basin, cf. Naish et al. (1998, doi:10.1016/S0277-3791(97)00075-9).

In situ pore water oxygen microprofiles from the Polar Front, Southern South Atlantic Ocean

Without doubt, global climate change is directly linked to the anthropogenic release of greenhouse gases such as carbon dioxide (CO2) and methane (UN IPCC-Report 2007). Therefore, research efforts to comprehend the global carbon cycle have increased during the last years. In the context of the observed changes, it is of particular interest to decipher the role of the hydro-, bio- and atmospheres and how the different compartments of the earth system are affected by the increase of atmospheric CO2. Due to its huge carbon inventory, the marine carbon cycle represents the most important component in this respect. Numerous findings suggest that the Southern Ocean plays a key role in terms of oceanic CO2 uptake. However, an exact quantification of such fluxes of material is hard to achieve for large areas, not least on account of the inaccessibility of this remote region. In particular, there exist so far only few accurate data for benthic carbon fluxes. The latter can be derived from high resolution pore water oxygen profiles, as one possible method. However the ex situ flux determinations carried out on sediment cores, tend to suffer from temperature and pressure artefacts. Alternatively, oxygen microprofiles can be measured in situ, i.e. at the seafloor. Until now, no such data have been published for the Southern Ocean. During the Antarctic Expedition ANT-XXI/4, within the framework of this thesis, in situ and ex situ oxygen profiles were measured and used to derive benthic organic carbon fluxes. Having both types of measurements from the same locations, it was possible to establish a depth-related correction function which was applied subsequently to revise published and additional unpublished carbon fluxes to the seafloor. This resulted in a consistent data base of benthic carbon inputs covering many important sub-regions of the Southern Ocean including the Amundsen and Bellingshausen Seas (southern Pacific), Scotia and Weddell Seas (southern South Atlantic) as well as the Crozet Basin (southern Indian Ocean). Including additional locations on the Antarctic Shelf, there are now 134 new and revised measurement locations, covering almost 180° of the Southern Ocean, for which benthic organic carbon fluxes and sedimentary oxygen penetration depth values are available. Further, benthic carbon fluxes were empirically related to dominant diatom distributions in surface sediments as well as to long-term remotely sensed chlorophyll-a estimates. The comparison of these results with benthic carbon fluxes of the entire Atlantic Ocean reveals significantly higher export efficiencies for the Southern Ocean than have previously been assumed, especially for the area of the opal belt.

(Table 1) Lithological and organic-geochemical compositions of bottom sediments from the Southwestern Indian Ocean (Mozambique Basin)

Geochemical changes in organic matter of bottom sediments from the Mozambique Basin at the river-sea barrier from the mouths of the Zambezi and Limpopo rivers toward the pelagic zone are discussed. Changes in bitumen, hydrolyzable material, humic acids, amino acids, n-alkanes, and polycyclic aromatic compounds resulting from genetic and diagenetic factors are described. This information is significant for paleoceanology reconstructions and for knowing ways of organic matter transformation into fossil forms.

Proxy calibration on two sedimentary sequences off Lisbon

High-resolution proxy data analyzed on two high-sedimentation shallow water sedimentary sequences (PO287-26B and PO287-28B) recovered off Lisbon (Portugal) provide the means for comparison to long-term instrumental time series of marine and atmospheric parameters (sea surface temperature (SST), precipitation, total river flow, and upwelling intensity computed from sea level pressure) and the possibility to do the necessary calibration for the quantification of past climate conditions. XRF Fe is used as proxy for river flow, and the upwelling-related diatom genus Chaetoceros is our upwelling proxy. SST is estimated from the coccolithophore-synthesized alkenones and Uk'37 index. Comparison of the Fe record to the instrumental data reveals its similarity to a mean average run of the instrumentally measured winter (JFMA) river flow on both sites. The upwelling diatom record concurs with the upwelling indices at both sites; however, high opal dissolution, below 20-25 cm, prevents its use for quantitative reconstructions. Alkenone-derived SST at site 28B does not show interannual variation; it has a mean value around 16°C and compares quite well with the instrumental winter/spring temperature. At site 26B the mean SST is the same, but a high degree of interannual variability (up to 4°C) appears to be determined by summer upwelling conditions. Stepwise regression analyses of the instrumental and proxy data sets provided regressions that explain from 65 to 94% of the variability contained in the original data, and reflect spring and summer river flow, as well as summer and winter upwelling indices, substantiating the relevance of seasons to the interpretation of the different proxy signals. The lack of analogs and the small data set available do not allow quantitative reconstructions at this time, but this might be a powerful tool for reconstructing past North Atlantic Oscillation conditions, should we be able to find continuous high-resolution records and overcome the analog problem.