Description: The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR). Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS). Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Description: Iron reduction is one of the most ancient forms of microbial respiration. This and the observation that iron reducers can grow under high temperature and pressure conditions suggests that they may play an important role in the deep biosphere. We will use stable Fe isotopes to disentangle microbial and abiotic processes involved in deep Fe cycling at IODP Site C0023 in the Nankai Trough. This will help to reach the goal of Expedition 370: ”T-Limit of the Deep Biosphere off Muroto” – the assessment of how microbial communities change with increasing sediment depth and temperature, by which factors changes are controlled, and where microbial life ceases. Dissolved iron was found at Site C0023 only within the methanic zone from 400 to 600 mbsf. The total drilling depth was 1180 mbsf. Is the Fe2+ release coupled to microbial activity? If yes, is it confined to the 200 m thick interval due to presence of reactive Fe minerals or because the microbes cannot cope with the temperatures prevailing in deeper sediments? Microbial iron reduction is known to cause pronounced enrichments of 54Fe in pore water, which should also be reflected by authigenic Fe minerals. The residual Fe pool, in contrast, becomes progressively enriched in 56Fe. Kinetic reactions of iron with sulfide enrich 56Fe in pore water, which allows a discrimination between microbial reduction and abiotic iron - sulfur interactions based on δ56Fe. As a result of different origins of incorporated Fe and different reactivities towards microbial reduction and sulfidation, Fe minerals in sediments possess different δ56Fe signatures and may show geochemical indications for microbial life. By analyzing δ56Fe of pore water and sequentially leached reactive and refractive Fe phases from Site C0023 sediments we will gain insight into the processes driving Fe2+ liberation at depth and hopefully assess links between the microbial activity and mineralogy (the presence of electron acceptors) as well as temperature.

Description: Sediments of sub-Antarctic islands have been proposed to be important contributors to natural iron fertilization in the Southern Ocean [1, 2]. This potential contribution depends on biogeochemical processes within the sediment that may result in an iron benthic flux, most likely related to the degradation of organic matter (OM). Yet, the OM degradation pathways vary strongly among different sedimentary settings. We elucidate the role of environmental factors on the prevailing biogeochemical pathways and reaction rates at three contrasting sites of South Georgia, using comprehensive solid-phase and pore-water analyses, as well as transportreaction modelling. Samples were obtained along a transect from a glacial fjord towards the shelf during cruise ANTXXIX/ 4 of RV POLARSTERN in 2013. Oxygen penetration depth at all sites is 〈1 cm. Sediments recovered within the fjord are dominated by dissimilatory iron reduction (DIR) and show very high dissolved Fe2+ concentrations of up to 760 μM, while sulfide was not detected. In addition, Fe reduction below the sulfate/methane transition was observed. High input of reactive iron phases, possibly enhanced by bioturbation and bubble ebullition, appear to favour DIR as the dominant metabolic process for OM degradation in the basin like fjord. Shelf sediments outside the fjord are sulfidic throughout, with H2S formed primarily by anaerobic oxidation of methane. The conversion of Fe oxides into Fe sulfides significantly alters the initial sediment composition along the shelf, and impact the availability of iron to the water column. OM is of marine origin at all three sites (C:N~7), indicating that Fe oxide availability and reactivity rather than the carbon source determine whether iron or sulfate reduction dominantes. [1] Moore & Braucher (2008) Biogeosciences 5, 631-656. [2] Borrione et al., (2014) Biogeosciences 11, 1981–2001.

Description: Iron fluxes from reducing sediments and subglacial environments are potential sources of bioavailable iron into the Southern Ocean. Stable iron isotopes are considered a proxy for Fe sources, but respective data are scarce and Fe cycling in complex natural environments is not understood sufficiently to constrain respective δ56Fe “endmembers” for different types of sediments, environmental conditions and biogeochemical processes. We show δ56Fe data from pore waters and sequentially leached solid Fe (for method see [1]) of two contrasting sites in a bay of King George Island that is affected by fast glacier retreat. Sediments close to the glacier front contain more reactive Fe oxides and pyrite compared to those close to the ice-free beach and show a broader ferruginous zone. Since sulfate reduction (SR) is almost negligible at this site, the pyrite likely derives from eroded bedrock. Interestingly, 56Fe depletion in pore water and most reactive Fe oxides is more pronounced close to the ice-free beach where SR was observed at shallow sediment depth. Downcore δ56Fe variability close to the glacier front is limited to surface-reduced Fe, whereas it also occurs in the ferrihydrite-lepidocrocite fraction station close to the ice-free beach. The ferrihydrite-lepidocrocite fraction is at least 0.5‰ lighter than goethite-hematite and magnetite at both sites indicating that it incorporates Fe that previously underwent redox cycling. High amounts of easily reducible Fe oxides, esp. at the glacier site, stimulate dissimilatory iron reduction (DIR) and prevent the use of less reactive Fe oxides. We infer that pyrite oxidation (subglacially or within the deposited sediment in the bay) and/or Fe2+ supply from subglacial environments promote Fe cycling and that DIR-dominated sediments do not necessarily result in isotopically lighter Fe fluxes compared to SR-dominated sediments. [1] Henkel et al. (2016), Chem. Geol. 421, 93-102.

Description: In 2016, International Ocean Discovery Program (IODP) Expedition 370 drilled Site C0023 in the Nankai Trough, off Cape Muroto (Shikoku Island, Japan, NW Pacific Ocean) [1]. The aim of this expedition was to explore the limits of life in the deep subseafloor sediments in a high temperature environment (up to 120°C), and to investigate, among other objectives, the processes at the biotic-abiotic transition. A deep sulfate-methane transition zone (SMTZ) was identified between 630 and 750 meters below sea floor (mbsf). Based on the magnetic data profiles and results from previous ODP expeditions in the area, four magnetic zones were defined mostly reflecting changes in detrital supply and alteration/diagenetic features. Here, a rock magnetic study is conducted in order to document the downhole changes in magnetic properties and magnetic mineralogy (content, grain size and composition of the magnetic mineral assemblage) related to post-depositional diagenetic processes from 200 to 1100 mbsf, with a focus on the deep SMTZ. Natural remanent magnetization and its alternating-field demagnetization, magnetic susceptibility and acquisition of isothermal remanent magnetization are measured on 225 discrete samples for concentration and composition of the magnetic assemblage. Hysteresis properties and first order reversal curves are measured on respective dry powders for magnetic grain size study and composition of the magnetic assemblage. The preliminary rock magnetic results are presented and discussed based on the shipboard inorganic geochemical data. They will be compared to another identified deep SMTZ at IODP Expedition 350 Site U1437 in the Izu Bonin rear arc (NW Pacific Ocean). [1] Heuer, V. et al. (2017) Expedition 370 Preliminary Report. International Ocean Discovery Program. http://dx.doi.org/10.14379/iodp.pr.370.2017

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: International Ocean Discovery Program (IODP) Expedition 370 aimed to explore the limits of life in the deep subseafloor biosphere at a location where temperature increases with depth at an intermediate rate and exceeds the known temperature maximum of microbial life (~120°C) at the sediment/basement interface ~1.2 km below the seafloor. Drilling Site C0023 is located in the vicinity of Ocean Drilling Program (ODP) Sites 808 and 1174 at the protothrust zone in the Nankai Trough off Cape Muroto at a water depth of 4776 m. ODP Leg 190 in 2000, revealed the presence of microbial cells at Site 1174 to a depth of ~600 meters below seafloor (mbsf), which corresponds to an estimated temperature of ~70°C, and reliably identified a single zone of higher cell concentrations just above the décollement at around 800 mbsf, where temperature presumably reached 90°C; no cell count data was reported for other sediment layers in the 70°–120°C range, because the limit of manual cell count for low-biomass samples was not high enough. With the establishment of Site C0023, we aimed to detect and investigate the presence or absence of life and biological processes at the biotic–abiotic transition with unprecedented analytical sensitivity and precision. Expedition 370 was the first expedition dedicated to subseafloor microbiology that achieved time-critical processing and analyses of deep biosphere samples by simultaneous shipboard and shore-based investigations. Our primary objectives during Expedition 370 were to study the relationship between the deep subseafloor biosphere and temperature. We aimed to comprehensively study the factors that control biomass, activity, and diversity of microbial communities in a subseafloor environment where temperatures increase from ~2°C at the seafloor to ~120°C at the sediment/basement interface and thus likely encompasses the biotic–abiotic transition zone. We also aimed to determine geochemical, geophysical, and hydrogeological characteristics in sediment and the underlying basaltic basement and elucidate if the supply of fluids containing thermogenic and/or geogenic nutrient and energy substrates may support subseafloor microbial communities in the Nankai accretionary complex. To address these primary scientific objectives and questions, we penetrated 1180 m and recovered 112 cores across the sediment/basalt interface. More than 13,000 samples were collected, and selected samples were transferred to the Kochi Core Center by helicopter for simultaneous microbiological sampling and analysis in laboratories with a super-clean environment. Following the coring operations, a temperature observatory with 13 thermistor sensors was installed in the borehole to 863 mbsf.