Description: Numerous studies have provided compelling evidence that the Pacific Ocean has experienced substantial glacial/interglacial changes in bottom-water oxygenation associated with enhanced carbon dioxide storage in the glacial deep ocean. Under postulated low glacial bottom-water oxygen concentrations (O2bw), redox zonation, biogeochemical processes and element fluxes in the sediments must have been distinctively different during the last glacial period (LGP) compared to current well-oxygenated conditions. In this study, we have investigated six sites situated in various European contract areas for the exploration of polymetallic nodules within the Clarion-Clipperton Zone (CCZ) in the NE Pacific and one site located in a protected Area of Particular Environmental Interest (APEI3) north of the CCZ. We found bulk sediment Mn maxima of up to 1 wt% in the upper oxic 10 cm of the sediments at all sites except for the APEI3 site. The application of a combined leaching protocol for the extraction of sedimentary Mn and Fe minerals revealed that mobilizable Mn(IV) represents the dominant Mn(oxyhydr)oxide phase with more than 70% of bulk solid-phase Mn. Steady state transport-reaction modeling showed that at postulated glacial O2bw of 35 µM, the oxic zone in the sediments was much more compressed than today where upward diffusing pore-water Mn2+ was oxidized and precipitated as authigenic Mn(IV) at the oxic-suboxic redox boundary in the upper 5 cm of the sediments. Transient transport-reaction modeling demonstrated that with increasing O2bw during the last glacial termination to current levels of ~ 150 µM, (1) the oxic-suboxic redox boundary migrated deeper into the sediments and (2) the authigenic Mn(IV) peak was continuously mixed into subsequently deposited sediments by bioturbation causing the observed mobilizable Mn(IV) enrichment in the surface sediments. Such a distinct mobilizable Mn(IV) maximum was not found in the surface sediments of the APEI3 site, which indicates that the oxic zone was not as condensed during the LGP at this site due to two- to threefold lower organic carbon burial rates. Leaching data for sedimentary Fe minerals suggest that Fe(III) has not been diagenetically redistributed during the LGP at any of the investigated sites. Our results demonstrate that the basin-wide deoxygenation in the NE Pacific during the LGP was associated with (1) a much more compressed oxic zone at sites with carbon burial fluxes higher than 1.5 mg Corg m-2 d-1, (2) the authigenic formation of a sub-surface mobilizable Mn(IV) maximum in the upper 5 cm of the sediments and (3) a possibly intensified suboxic-diagenetic growth of polymetallic nodules. As our study provides evidence that authigenic Mn(IV) precipitated in the surface sediments under postulated low glacial O2bw, it contributes to resolving a long-standing controversy concerning the origin of widely observed Mn-rich layers in glacial/deglacial deep-sea sediments.

Description: Iron formations (IFs) are important geochemical repositories that provide constraints on atmospheric and ocean chemistry, prior to and during the onset of the Great Oxidation Event. Trace metal abundances and their Mo-Cr- U isotopic ratios have been widely used for investigating ocean redox processes through the Archean and Paleoproterozoic. Mineralogically, IFs consist of three main Fe-bearing fractions: (1) Fe-Ca-Mg-Mn carbonates, (2) magnetite and/or hematite and (3) Fe-silicates. These fractions are typically fine-grained on a sub-μm scale and their co-occurrence in varying amounts means that bulk-rock or microanalytical geochemical and stable isotope data can be influenced by cryptic changes in mineralogy. Fraction specific geochemical analysis has the potential to resolve mineralogical controls and reveal diagenetic versus primary precipitative controls on IF mineralogy. Here we adapt an existing sequential extraction scheme for Fe-phases (Poulton and Canfield, 2005) to the high Fe-content in IF and the specific three-fraction mineralogy. We optimized the scheme for magnetite-dominated Archean IFs using samples from the hematite-poor Asbestos Hills Subgroup IF, Transvaal Supergroup, South Africa. Previously commonly-used hydroxylamine-HCl and dithionite leaches were omitted since ferric oxides are quantitatively insignificant in these IF samples. The acetate leach was tested at variable temperatures, reaction times and under different atmospheres in order to ensure that all micro-crystalline Fe-carbonates were effectively dissolved, resulting in an optimum extraction for 48 h at 50 °C under anoxic conditions. The dissolution of magnetite by NH4-oxalate was also tested, resulting in an optimum extraction for 24 h under an ambient atmosphere. Finally, a HF-HClO4-HNO3 leach was used to dissolve the residual silicate fraction which has to date not been considered in detail in IF. Accuracy of the extraction technique was generally excellent, as verified using 1) elemental recoveries, 2) comparison of major and trace element distributions against mineralogy and 3) comparison to results from microanalytical techniques. This study focuses on the distribution of three frequently used geochemical proxies in IF; U, Mo and Cr. Molybdenum abundances in the Kuruman and Griquatown IF are low and show an apparent correlation with mineralogical variability, as determined by the sequential extraction. This suggests that changes in bulk-rock mineralogy, rather than redox chemistry might significantly affect Mo stable isotopes. For Cr, a minor bulk-rock stratigraphic increase can be related to the oxide and silicate fraction. However, a positive relationship with Zr indicates that this was also controlled by detrital or volcanic ash input. Uranium is predominantly bound to the silicate fraction and shows clear correlations with Zr and Sc implying detrital reworking under anoxic conditions. The discrepant behaviour of these three proxies indicate that mineralogy should be taken into account when interpreting heterogeneous bulk-rock samples and that fraction specific techniques will provide new insights into the evolution of atmosphere and ocean chemistry.

Description: The Argentina Continental Margin represents a unique geologic setting where fundamental interactions between bottom currents and sediment deposition as well as their impact on biogeochemical processes and element cycling, in particular iron, can be studied. The aims of this study were to investigate 1) the consequences of different depositional conditions on biogeochemical processes and 2) diagenetic cycling of Fe mineral phases in surface sediments. Furthermore, it was 3) studied how sedimentary stable Fe isotope signatures (δ56Fe) are affected during early diagenesis and finally 4) evaluated, under which conditions δ56Fe might be used as proxy for microbial Fe reduction in methanic sediments. During RV SONNE expedition SO260, carried out in the framework of the DFG-funded Cluster of Excellence “The Ocean in the Earth System”, surface sediments from two depositional environments were sampled each using gravity corer and multi corer. One study site is located on the lower continental slope at 3605 m water depth (Biogeochemistry Site), while the other site is situated in a contourite system on the Northern Ewing Terrace at 1078 m water depth (Contourite Terrace Site). Sequential Fe extractions were performed on the collected sediments to determine four operationally defined reactive Fe phases targeting Fe carbonates, (easily) reducible Fe (oxyhydr)oxides and hardly reducible Fe oxides [1]. Purification of extracts for δ56Fe analysis of the Fe carbonates and easily reducible Fe (oxyhydr)oxide fractions followed [2]. The dataset was combined with pore-water data obtained during the cruise and complemented by concentrations and stable carbon isotope signatures of dissolved methane determined post-cruise. The extent of the redox zonation and depth of the sulfate-methane-transition (SMT) differ between the two sites. It is suggested that sedimentation rates at the Biogeochemistry Site are low and that steady state conditions prevail, leading to a strong diagenetic overprint of sedimentary Fe phases. In contrast the Contourite Terrace Site is characterized by high sedimentation rates and a lack of pronounced diagenetic overprint [3]. Reactive Fe phases are subject to reductive dissolution at the SMT. Nevertheless, significant amounts of reactive Fe phases are preserved below the SMT as evidenced by the presence of dissolved Fe in the methanic sediments, and are available for deep Fe reduction possibly through Fe-mediated anaerobic oxidation of methane [4]. In this study, δ56Fe signatures of reactive Fe phases in methanic sediments were determined for the first time. These data suggest significant microbial fractionation of Fe isotopes during deep Fe reduction at the Biogeochemistry Site, whereas at the Contourite Terrace Site the δ56Fe signatures do not indicate remarkable microbial Fe isotope fractionation. It is concluded that the applicability of δ56Fe signatures as tracer for microbial Fe reduction might be sensitive to the depositional regime, and thus may be limited in high sedimentation areas. References: [1]Poulton SW and Canfield DE, 2005. Chemical Geology 214: 209-221. [2]Henkel, S. et al., 2016. Chemical Geology 421: 93-102. [3]Riedinger, N. et al., 2005. Geochimica et Cosmochimica Acta 69: 4117-4126. [4]Riedinger, N. et al., 2014. Geobiology 12: 172-181.