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: Mössbauer spectroscopic investigations of deep-sea sediments from the Peru Basin revealed a prominent downcore increase of the bulk sediment Fe(II)/Fe(III) ratio across the well-known tan-green color transition. This increase occurs along a continuous gradient extending over a 3 cm zone at the two deep-sea sites that we report. Remarkably constant values of the Fe(II)/Fe(III) ratios above (11 ± 2%/89 ± 2%) and below (37 ± 2%/63 ± 2%) the iron redox transition-zone delimit the gradient clearly. A minor peak of diagenetic iron enrichment is manifest at the redox front. This Fe enrichment has accumulated in a redox cycle and amounts to 16 ± 4% of the total Fe at the peak maximum. The data imply that 26 ± 4% of the detrital iron has experienced in situ redox transition from Fe(III) to Fe(II) within the iron redox transition-zone.

Description: A geochemical model of the Peru Basin deep-sea floor, based on an extensive set of field data as well as on numerical simulations, is presented. The model takes into account the vertical oscillations of the redox zonation that occur in response to both long-term (glacial/interglacial) and short-term (El Niño Southern Oscillation (ENSO) time scale) variations in the depositional flux of organic matter. Field evidence of reaction between the pore water NO3− and an oxidizable fraction of the structural Fe(II) in the clay mineral content of the deep-sea sediments is provided. The conditions of formation and destruction of reactive clay Fe(II) layers in the sea floor are defined, whereby a new paleo-redox proxy is established. Transitional NO3− profile shapes are explained by periodic contractions and expansions of the oxic zone (ocean bottom respiration) on the ENSO time scale. The near-surface oscillations of the oxic–suboxic boundary constitute a redox pump mechanism of major importance with respect to diagenetic trace metal enrichments and manganese nodule formation, which may account for the particularly high nodule growth rates in this ocean basin. These conditions are due to the similar depth ranges of both the O2 penetration in the sea floor and the bioturbated high reactivity surface layer (HRSL), all against the background of ENSO-related large variations in depositional Corg flux. Removal of the HRSL in the course of deep-sea mining would result in a massive expansion of the oxic surface layer and, thus, the shut down of the near-surface redox pump for centuries, which is demonstrated by numerical modeling.

Description: Mössbauer spectroscopy was applied to characterize the valence states Fe(II) and Fe(III) in sedimentary minerals from a core of the Peru Basin. The procedure in unraveling this information includes temperature-dependent measurements from 275 K to very low temperature (300 mK) in zero–field and also at 4.2 K in an applied field (up to 6.2 T) and by mathematical procedures (least-squares fits and spectral simulations) in order to resolve individual spectral components. The depth distribution of the amount of Fe(II) is about 11% of the total Fe to a depth of 19 cm with a subsequent steep increase (within 3 cm) to about 37%, after which it remains constant to the lower end of the sediment core (at about 40 cm). The steep increase of the amount of Fe(II) defines a redox boundary which coincides with the position where the tan/green color transition of the sediment occurs. The isomer shifts and quadrupole splittings of Fe(II) and Fe(III) in the sediment are consistent with hexacoordination by oxygen or hydroxide ligands as in oxide and silicate minerals. Goethite and traces of hematite are observed only above the redox boundary, with a linear gradient extending from about 20% of the total Fe close to the sediment surface to about zero at the redox boundary. The superparamagnetic relaxation behavior allows to estimate the order of magnitude for the size of the largest goethite and hematite particles within the particle-site distribution, e.g. ∼170 Å and ∼50 Å, respectively. The composition of the sediment spectra recorded at 300 mK in zero-field, apart from the contributions due to goethite and hematite, resembles that of the sheet silicates smectite, illite and chlorite, which have been identified as major constituents of the sediment in the 〈2 μm fraction by X-ray diffraction. The specific “ferromagnetic” type of magnetic ordering in the sediment, as detected at 4.2 K in an applied field, also resembles that observed in sheet silicates and indicates that both Fe(II) and Fe(III) are involved in magnetic ordering. This “ferromagnetic” behavior is probably due to the double-exchange mechanism known from other mixed-valence Fe(II)–Fe(III) systems. A significant part of the clay-mineral iron is redox sensitive. It is proposed that the color change of the sediment at the redox boundary from tan to green is related to the increase of Fe(II)–Fe(III) pairs in the layer silicates, because of the intervalence electron transfer bands which are caused by such pairs.

Description: The percentage of the structural Fe(II) in clay minerals that is readily oxidized to Fe(III) upon contact with atmospheric oxygen was determined across the downcore tan–green color change in Peru Basin sediments. This latent fraction of reactive Fe(II) was only found in the green strata, where it proved to be large enough to constitute a deep reaction layer with respect to the pore water O2 and NO3−. Large variations were detected in the proportion of the reactive Fe(II) concentration to the organic matter content along core profiles. Hence, the commonly observed tan–green color change in marine sediments marks the top of a reactive Fe(II) layer, which may represent the major barrier to the movement of oxidation fronts in pelagic subsurface sediments. This is also demonstrated by numerical model simulations. The findings imply that geochemical barriers to pore water oxidation fronts form diagenetically in the sea floor wherever the stage of iron reduction is reached, provided that the sediments contain a significant amount of structural iron in clay minerals.