Geochemistry of continental slope and deep sea basin sediments off Uruguay

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement (<6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1 N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24 h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe2+. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.

Revised composite depth scale, Fe content and orbital tuning of Middle Eocene Climate Optimum samples from ODP Site 207-1260

A high-resolution stratigraphy is essential toward deciphering climate variability in detail and understanding causality arguments of events in earth history. Because the highly dynamic middle to late Eocene provides a suitable testing ground for carbon cycle models for a waning warm world, an accurate time scale is needed to decode climate-driving mechanisms. Here we present new results from ODP Site 1260 (Leg 207) which covers a unique expanded middle Eocene section (magnetochrons C18r to C20r, late Lutetian to early Bartonian) of the tropical western Atlantic including the chron C19r transient hyperthermal event and the Middle Eocene Climate Optimum (MECO). To establish a detailed cyclostratigraphy we acquired a distinctive iron intensity records by XRF scanning Site 1260 cores. We revise the shipboard composite section, establish a cyclostratigraphy and use the exceptional eccentricity modulated precession cycles for orbital tuning. The new astrochronology revises the age of magnetic polarity chrons C19n to C20n, validates the position of very long eccentricity minima at 40.2 and 43.0 Ma in the orbital solutions, and extends the Astronomically Tuned Geological Time Scale back to 44 Ma. For the first time the new data provide clear evidence for an orbital pacing of the chron C19r event and a likely involvement of the very long eccentricity cycle contributing to the evolution of the MECO.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.