Description: Changes in bulk sediment Fe(II)/Fe(III) ratio and in the distribution of iron among different minerals as a result of Ocean Drilling Program archive storage in the Bremen Core Repository were investigated using Mössbauer spectroscopy. Massive Fe(II) to Fe(III) oxidation, which involved between 24% and 45% of the initial Fe(II), occurred within only 6 months of refrigerated storage. Prior to archive storage, 〉95% of the Fe(II) in the sediment samples under investigation was structural iron in silicate minerals. Hence, virtually the entire oxidation process took place within silicate mineral lattices, and the sediment mineral assemblage was not changed in this case. Nevertheless, the observed oxidation of the comparatively shielded silicate lattice Fe(II) suggests that Fe(II) bound in authigenic carbonates, phosphates, or sulfides - such as that found in many marine sediments - would likely be oxidized at least as fast. Those minerals, however, would be replaced by Fe(III)-bearing oxides and oxyhydroxides, which implies a change of sediment composition, and thus, of various sediment properties, including the magnetic signal, within a few months of storage. Furthermore, changes in the silicate lattice Fe(II)/Fe(III) ratio during storage, such as those reported here, also signify loss of information. This is because oxidation of the structural Fe(II) upon contact with atmospheric oxygen may occur only inasmuch as the inverse Fe(III)-Fe(II) redox transition has taken place in the seabed. Therefore, the reversible shift, if it were measured under controlled reoxidation in the laboratory, may suggest the chemical stress that was suffered by the iron oxide minerals at the ocean bottom. Concerning Site 1062, this process might help to judge both the authenticity of magnetic field excursion records and the lithostratigraphic value of red lutites at given sediment depths. Although the nature and extent of information loss or alteration during storage depend on sediment type, the reported observations emphasize the need for special sample protection with respect to properties that might be affected.

Description: The sediments recovered on ODP Leg 104 have been reported to be characterized by hiatuses. The hiatuses were defined by biostratigraphy and were believed to be caused by erosion related to temporary changes of bottom current composition and velocity. They have been associated with major paleoenvironmental changes, reorganization of global deep water production, and increased bottom water flows. Because of the importance of hiatuses for ongoing research, we decided to closely investigate the sedimentation history for the most significant Pliocene and Miocene biostratigraphic hiatuses by sedimentologic and geochemical means. The sedimentologic studies include clay mineral distributions, grain size data, and organic carbon concentrations. The geochemical studies include determination of 87/86Sr ratios, 10Be and Ir concentrations. The results of the sedimentologic studies suggest either that paleoenvironmental changes associated with hiatuses are not represented in the preserved sediments, or that the hiatuses are an artifact of interpretation of the biostratigraphic data. Strontium isotopes indicate continuous sedimentation for the interval investigated at Site 642, an interpretation confirmed by the steady decline in 10Be. 87/86Sr ratios in the interval from above and below proposed hiatuses H 2.2/2.3 and H2.1/2.2 at Site 643 display stronger changes with depth than expected by steady sedimentation. Ir data for this same interval indicate reduced sedimentation rates. Combining both, sedimentologic and geochemical evidence, the proposed hiatuses could not be confirmed and may represent preservation artifacts.