Average fluorescence and dissolved iron and Fe-binding ligand characteristics during POLARSTERN expedition ANT-XXIV/3 in 2008

Organic complexation of dissolved iron (dFe) was investigated in the Atlantic sector of the Southern Ocean in order to understand the distribution of Fe over the whole water column. The total concentration of dissolved organic ligands ([Lt]) measured by voltammetry ranged between 0.54 and 1.84 nEq of M Fe whereas the conditional binding strength (K') ranged between 10**21.4 and 10**22.8. For the first time, trends in Fe-organic complexation were observed in an ocean basin by examining the ratio ([Lt]/[dFe]), defined as the organic ligand concentration divided by the dissolved Fe concentration. The [Lt]/[dFe] ratio indicates the saturation state of the natural ligands with Fe; a ratio near 1 means saturation of the ligands leading to precipitation of Fe. Reversely, high ratios mean Fe depletion and show a high potential for Fe solubilisation. In surface waters where phytoplankton is present low dissolved Fe and high variable ligand concentrations were found. Here the [Lt]/[dFe] ratio was on average 4.4. It was especially high (5.6-26.7) in the HNLC (High Nutrient, Low Chlorophyll) regions, where Fe was depleted. The [Lt]/[dFe] ratio decreased with depth due to increasing dissolved Fe concentrations and became constant below 450 m, indicating a steady state between ligand and Fe. Relatively low [Lt]/[dFe] ratios (between 1.1 and 2.7) existed in deep water north of the Southern Boundary, facilitating Fe precipitation. The [Lt]/[dFe] ratio increased southwards from the Southern Boundary on the Zero Meridian and from east to west in the Weddell Gyre due to changes both in ligand characteristics and in dissolved iron concentration. High [Lt]/[dFe] ratio expresses Fe depletion versus ligand production in the surface. The decrease with depth reflects the increase of [dFe] which favours scavenging and (co-) precipitation, whereas a horizontal increase in the deep waters results from an increasing distance from Fe sources. This increase in the [Lt]/[dFe] ratio at depth shows the very resistant nature of the dissolved organic ligands.

Iron and carbon geochemistry of sediment core GeoB1401-4

Iron speciation was determined in hemiplegic sediments from a high productivity area to investigate systematically the early diagenetic reactivity of Fe. A combination of various leaching agents (1 M HCI, dithionite buffered in citrate/acetic acid, HF/H2SO4, acetic Cr(II)) was applied to sediment and extracted more than 80% of total Fe. Subsequent Fe species determination defined specific mineral fractions that are available for Fe reduction and fractions formed as products of Fe diagenesis. To determine the Fe speciation of (sheet) silicates we explored an extraction procedure (HF/H2SO4) and verified the procedure by application to standard rocks. Variations of Fe speciation of (sheet) silicates reflect the possible formation of Fe-bearing silicates in near surface sediments. The same fraction indicates a change in the primary input at greater depth, which is supported by other parameters. The Fe(II)/ Fe(III) -ratio of total sediment determined by extractions was compared with Mössbauer-spectroscopy ] at room temperature and showed agreement within 10%. M6ssbauer-spectroscopy indicates the occurrence of siderite in the presence of free sulfide and pyrite, supporting the importance of microenvironments during mineral formation. The occurrence of other Fe(II) bearing minerals such as ankerite (Ca-, Fe-, Mg-carbonate) can be presumed but remains speculative.

Susceptibility, density, iron and calcium concentrations of ODP holes 165-999B and 165-1001A

Pelagic sediments recording an extreme and short-lived global warming event, the Late Paleocene Thermal Maximum (LPTM), were recovered from Hole 999B (Colombian Basin) and Holes 1001A and 1001B (lower Nicaraguan Rise) in the Caribbean Sea during Ocean Drilling Program Leg 165. The LPTM consists of a 0.3-0.97 m calcareous claystone to claystone horizon. High-resolution downhole logging (Formation MicroScanner [FMS]), standard downhole logs (resistivity, velocity, density, natural gamma ray, and geochemical log), and non-destructive chemical and physical property (multisensor core logger [MSCL] and X-ray fluorescence [XRF] core scanner) data were used to identify composite sections from parallel holes and to record sedimentological and environmental changes associated with the LPTM. Downhole logging data indicate an abrupt and distinct difference in physical and chemical properties that extend for tens of meters above and below the LPTM. These observations indicate a rapid environmental change at the LPTM, which persists beyond the LPTM anomaly. Comparisons of gamma-ray attenuation porosity evaluator (GRAPE) densities from MSCL logging on split cores with FMS resistivity values allows core-to-log correlation with a high degree of accuracy. High-resolution magnetic susceptibility measurements of the cores are compared with elemental concentrations (e.g., Fe, Ca) analyzed by high-resolution XRF scanning. The high-resolution data obtained from several detailed core and downhole logging methods are the key to the construction of composite sections, the correlation of both adjacent holes and distant sites, and core-log integration. These continuous-depth series reveal the LPTM as a multiphase event with a nearly instantaneous onset, followed by a much different set of physical and chemical conditions of short duration, succeeded by a longer transition to a new, more permanent set of environmental circumstances. The estimated duration of these 'phases' are consistent with paleontological and isotopic studies of the LPTM