Geochemistry of sediment core HE337/001-1, North Sea

Reactive iron (oxyhydr)oxide minerals preferentially undergo early diagenetic redox cycling which can result in the production of dissolved Fe(II), adsorption of Fe(II) onto particle surfaces, and the formation of authigenic Fe minerals. The partitioning of iron in sediments has traditionally been studied by applying sequential extractions that target operationally-defined iron phases. Here, we complement an existing sequential leaching method by developing a sample processing protocol for d56Fe analysis, which we subsequently use to study Fe phase-specific fractionation related to dissimilatory iron reduction in a modern marine sediment. Carbonate-Fe was extracted by acetate, easily reducible oxides (e.g. ferrihydrite and lepidocrocite) by hydroxylamine-HCl, reducible oxides (e.g. goethite and hematite) by dithionite-citrate, and magnetite by ammonium oxalate. Subsequently, the samples were repeatedly oxidized, heated and purified via Fe precipitation and column chromatography. The method was applied to surface sediments collected from the North Sea, south of the Island of Helgoland. The acetate-soluble fraction (targeting siderite and ankerite) showed a pronounced downcore d56Fe trend. This iron pool was most depleted in 56Fe close to the sediment-water interface, similar to trends observed for pore-water Fe(II). We interpret this pool as surface-reduced Fe(II), rather than siderite or ankerite, that was open to electron and atom exchange with the oxide surface. Common extractions using 0.5 M HCl or Na-dithionite alone may not resolve such trends, as they dissolve iron from isotopically distinct pools leading to a mixed signal. Na-dithionite leaching alone, for example, targets the sum of reducible Fe oxides that potentially differ in their isotopic fingerprint. Hence, the development of a sequential extraction Fe isotope protocol provides a new opportunity for detailed study of the behavior of iron in a wide-range of environmental settings.

Sedimentology of core M74/4_1143-1

Periplatform ooze is an admixture of pelagic carbonate and sediment derived from neritic carbonate platforms. Compositional variations of periplatform ooze allow the rectonstruction of past sea-level changes. Periplatform ooze formed during sea-level highstands is finer grained and richer in aragonit through the elevated input of material from the flooded platform compared to periplatform ooze formed during the episodes of lowered sea level. In many cases, however, the sea floor around carbonate platforms is subjected to bottom currents which are expected to affect sediment composition, i.e. through winnowing of the fine fraction. The interaction of sea-level driven highstand shedding and current impact on the formation of periplatform ooze is influenced or even distorted by changing current activity, an integrated study using seismic, hydroacoustic and sedimentological data has been performed on periplatform ooze deposited in the Inner Sea of the Maldives. The Miocene to Pleistocene succession of drift deposits is subdivided into nine units; limits of seismostratigraphic units correspond to changes or turnarounds in grain size trends in cores recovered at ODP Site 716 and NEOMA Site 1143. For the Pleistocene it can be shown how changes in grain size occur in concert with sea-level changes and changes of the monsoonal system, which is thought to be a major driver bottom currents in the Maldives. A clear hightstand shedding pattern only appears in the data at a time of of relaxation of monsoonal strength during the last 315 ky. Results imply (1) that drift sediments provide a potential target for analyzing past changes in oceanic currents and (2) that the ooze composition bears a mixed signal of input and physical winnowing at the sea floor.