Detailed analysis of the organic carbon content in sediment cores M0002 and M0004

During IODP Expedition 302 (Arctic Coring Expedition-ACEX), the first scientific drilling campaign in the permantly ice-covered central Arctic Ocean, a 430 m thick sequence of upper Cretaceaous to Quaternary sediments has been drilled. The lower half of this sequence is composed of organic-carbon-rich (black shale-type) sediments with total organic carbon contents of about 1-14%. Significant amounts of the organic matter preserved in these sediments is of algae-type origin and accumulated under anoxic/euxinic conditions. Here, for the first time detailed data on the source-rock potential of these black shales are presented, indicating that most of the Eocene sediments have a (fair to) good source-rock potential, prone to generate a gas/oil mixture. The source-rock potential of the Campanian and upper Paleocene sediments, on the other hand, is rather low. The presence of oil or gas already generated in situ, however, can be ruled out due to the immaturity of the ACEX sediments.

X-ray fluorescence (XRF) scannings and grain size analysis at sites in the Gulf of Cádiz

Contourites in the Gulf of Cádiz preserve a unique archive of Mediterranean Outflow Water (MOW) variability over the past 5.3 Ma. In our study we investigate the potential of geochemical data obtained by XRF scanning to decipher bottom current processes and paleoclimatic evolution at two different sites drilled through contourite deposits in the northern Gulf of Cadiz: Site U1387, which is bathed by the upper MOW core, and Site U1389, located more proximal to the Straits of Gibraltar. The lack of major downslope transport at both locations during the Pleistocene makes them ideal locations for the purpose of our study. The results indicate that the Zr/Al ratio, representing the relative enrichment of heavy minerals (zircon) over less dense alumosilicates under strong bottom current flow, is the most useful indicator for a semi-quantitative assessment of current strength. While most elements are biased by current-related processes, the bromine record, representing organic content, preserves the most pristine climate signal rather independent of grain size changes. Hence, Br can be used for chronostratigraphy and site-to-site correlation in addition to stable isotope stratigraphy. Based on these findings we reconstructed MOW variability for Marine Isotope Stages 1-5 using the Zr/Al ratio from Site U1387. The results reveal abrupt, millennial-scale variations of MOW strength during Greenland Stadials (GS) and Interstadials (GI) with strong MOW during GS and glacial Terminations and a complex behavior during Heinrich Stadials. Millennial-scale variability persisting during periods of poorly expressed GS/GI cyclicities implies a strong internal oscillation of the Mediterranean/North Atlantic climate system.

Grain-size analysis and geochemistry of sediment core GeoB13602-1

Grain-size, terrigenous element and rock magnetic remanence data of Quaternary marine sediments retrieved at the NW African continental margin off Gambia (gravity core GeoB 13602-1, 13°32.71' N, 17°50.96'W) were jointly analyzed by end-member (EM) unmixing methods to distinguish and budget past terrigenous fluxes. We compare and cross-validate the identified single-parameter EM systems and develop a numerical strategy to calculate associated multi-parameter EM properties. One aeolian and two fluvial EMs were found. The aeolian EM is much coarser than the fluvial EMs and is associated with a lower goethite/hematite ratio, a higher relative concentration of magnetite and lower Al/Si and Fe/K ratios. Accumulation rates and grain sizes of the fluvial sediment appear to be primarily constrained by shore distance (i.e., sea-level fluctuations) and to a lesser extent by changes in hinterland precipitation. High dust fluxes occurred during the Last Glacial Maximum (LGM) and during Heinrich Stadials (HS) while the fluvial input remained unchanged. Our approach reveals that the LGM dust fluxes were ~7 times higher than today's. However, by far the highest dust accumulation occurred during HS 1 (~300 g m**-2 yr** -1), when dust fluxes were ~80 fold higher than today. Such numbers have not yet been reported for NW Africa, and emphasize strikingly different environmental conditions during HSs. They suggest that deflation rate and areal extent of HSs dust sources were much larger due to retreating vegetation covers. Beyond its regional and temporal scope, this study develops new, in principle, generally applicable strategies for multi-method end-member interpretation, validation and flux budgeting calibration.

Bulk geochemical analysis and planktonic foraminifera of sediment core GeoB7112-5

A multivariable approach utilising bulk sediment, planktonic Foraminifera and siliceous phytoplankton has been used to reconstruct rapid variations in palaeoproductivity in the Peru-Chile Current System off northern Chile for the past 19000 cal. yr. During the early deglaciation (19000-16000 cal. yr BP), our data point to strongest upwelling intensity and highest productivity of the past 19 000 cal. yr. The late deglaciation (16000-13000 cal. yr BP) is characterised by a major change in the oceanographic setting, warmer water masses and weaker upwelling at the study site. Lowest productivity and weakest upwelling intensity are observed from the early to the middle Holocene (13000-4000 cal. yr BP), and the beginning of the late Holocene (<4000 cal. yr BP) is marked by increasing productivity, mainly driven by silicate-producing organisms. Changes in the productivity and upwelling intensity in our record may have resulted from a large-scale compression and/or displacement of the South Pacific subtropical gyre during more productive periods, in line with a northward extension of the Antarctic Circumpolar Current and increased advection of Antarctic water masses with the Peru-Chile Current. The corresponding increase in hemispheric thermal gradient and wind stress induced stronger upwelling. During the periods of lower productivity, this scenario probably reversed.

Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the presence in the water column of a large fraction of seep derived ele- ments (e.g. approximately 50% of iron, over 80% of Mn, 100% of Cr, S and Zn) in the form of nano sized par- ticles (e.g. b100 nm) even at typical open ocean pHs. We launch in situ sampling protocols and sample preparation procedures for multi-method suitable to obtain accurate measurements on nanoparticles from environmental samples. Based on our results a first insight to the formation of natural nanoparticles at cold CO2 seeps is presented and the persistence of such nano-clusters in the surrounding seawater is stipulated.

Analysis of Mn-nodules from the Indian Ocean

This report studies the principal paramters governing the distribution of iron-manganese concretions on the sea floor of the Indian Ocean, as well as their petrography and mineralogy. The results are mainly based on the recoveries made during voyages 31, 33 and 35 of the "Vityaz"' (1959-1962) and partly during voyages 36 and 41 (1964-1966). During these voyages samples of Mn concretions and Mn crust were collected (by bottom grabs, cores, trawlings, and dredgings) at 39 stations. The following account is devoted to the problems concerning the geochemistry of these concretions.

Analysis of Recent benthic foraminiferal assemblages from the oxygen minimum zone of the Pakistan continental margin

Live (Rose Bengal stained) and dead benthic foraminiferal communities (hard-shelled species only) from the Pakistan continental margin oxygen minimum zone (OMZ) have been studied in order to determine the relation between faunal composition and the oxygenation of bottom waters. During R.R.S. Charles Darwin Cruises 145 and 146 (12 March to May 28 2003), 11 multicores were taken on the continental margin off Karachi, Pakistan. Two transects were sampled, constituting a composite bathymetric profile from 136 m (above the OMZ in spring 2003) down to 1870 m water depth. Cores (surface area 25.5 cm2) were processed as follows: for stations situated above, and in the upper part of the OMZ, sediment slices were taken for the 0-0.5 and 0.5-1 cm intervals, and then in 1 cm intervals down to 10 cm. For the lower part of the OMZ, the second centimetre was also sliced in half-centimetre intervals. Each sample was stored in 10 % borax-buffered formalin for further processing. Onshore, the samples were wet sieved over 63 µm, 150 µm and 300 µm sieves and the residues were stained for one week in ethanol with Rose Bengal. After staining, the residue was washed again. The stained faunas were picked wet in three granulometric fractions (63-150 µm, 150-300 µm and >300 µm), down to 10 cm depth. To gain more insight into the population dynamics we investigated the dead (unstained) foraminifera in the 2-3 cm level for the fractions 150-300 µm and >300 µm. The fractions >300 µm and 150-300 µm show nearly the same faunal distribution and therefore the results are presented here for both fractions combined (i.e. the >150 µm fraction). Live foraminiferal densities show a clear maximum in the first half centimetre of the sediment; only few specimens are found down to 4 cm depth. The faunas exhibit a clear zonation across the Pakistan margin OMZ. Down to 500 m water depth, Uvigerina ex gr. U. semiornata and Bolivina aff. B. dilatata dominate the assemblages. These taxa are largely restricted to the upper cm of the sediment. They are adapted to the very low bottom-water oxygen values (ab. 0.1 ml/l in the OMZ core) and the extremely high input of organic carbon on the upper continental slope. The lower part of the OMZ is characterized by cosmopolitan faunas, containing also some taxa that in other areas have been described in deep infaunal microhabitats.