Description: Biogeochemical processes in subseafloor sediments are closely coupled to global element cycles. To improve the understanding of changes in biogeochemical conditions on geological timescales, we investigate sediment cores from a 1180 m deep hole in the Nankai Trough offshore Japan (Site C0023) drilled during International Ocean Discovery Program Expedition 370. During its tectonic migration from the Shikoku Basin to the Nankai Trough over the past 15 Ma, Site C0023 has experienced significant changes in depositional, thermal, and geochemical conditions. By combining pore-water, solid-phase, and rock magnetic data, we demonstrate that a transition from organic carbon-starved conditions with predominantly aerobic respiration to an elevated carbon burial environment with increased sedimentation occurred at ∼2.5 Ma. Higher rates of organic carbon burial in consequence of increased nutrient supply and productivity likely stimulated the onset of anaerobic electron-accepting processes during organic carbon degradation. A significant temperature increase by ∼50°C across the sediment column associated with trench-style sedimentation since ∼0.5 Ma could increase the bioavailability of organic matter and enhance biogenic methanogenesis. The resulting shifts in reaction fronts led to diagenetic transformation of iron (oxyhydr)oxides into pyrite in the organic carbon-starved sediments several millions of years after burial. We also show that high amounts of reducible iron(III) which can serve as electron acceptor for microbial iron(III) reduction are preserved and still available as phyllosilicate-bound Fe. This is the first study that shows the evolution of long-term variations of (bio-)geochemical processes along tectonic migration of ocean floor, thereby altering the primary sediment composition long after deposition.

Description: Oceanic anoxic events (OAEs) were a frequent occurrence in the Cretaceous greenhouse ocean. Based on a variety of paleoredox indicators, euxinic water column conditions are commonly invoked for these OAEs. However, in a high resolution study of OAE3 deep sea sediments [1], revised paleoredox indicators suggest that euxinic conditions fluctuated with anoxic ferruginous conditions on orbital timescales. Building upon this, we here present new data for a continental shelf setting at Tarfaya, Morocco, that spans a period prior to, and during, the onset of OAE2. We again find strong evidence for orbital transitions from euxinic to ferruginous conditions. The presence of this distinct cyclicity during OAE2 and OAE3 in shallow and deep water settings, coupled with its occurrence on the anoxic shelf prior to the global onset of anoxia, suggests that these fluctuations were a fundamental feature of anoxia in the Cretaceous ocean. The observed redox cyclicity has major implications for the cycling of phosphorus, and hence the maintenance and longevity of OAEs. However, despite this significance, controls on the observed redox cyclicity are essentially unknown. Here, we utilize S isotope measurements (pyrite S and carbonate-associated S) from the deep sea and shelf settings to model oceanic sulphate concentrations across the redox transitions. Perhaps surprisingly, we find no evidence to suggest that ferruginous conditions arose due to extensive drawdown of seawater sulphate (as pyrite-S and organic-S) under euxinic conditions. Instead, S isotope systematics in the deep sea imply increased sulphate concentrations during ferruginous intervals. Based on these observations and other major element data, we infer that the redox cyclicity instead relates to orbitally-paced fluctuations in continental hydrology and weathering, linking the redox state of the global ocean to climate-driven processes on land. [1] März et al (2008) GCA, 72, 3703-3717.

Description: The partitioning of Fe in sediments and soils has traditionally been studied by applying sequential leaching methods. These are based on reductive dissolution and exploit differences in dissolution rates between different reactive Fe (oxyhydr)oxide minerals. We used lab-made ferrihydrite, goethite, hematite and magnetite spiked with 58Fe and leached two-mineral mixtures with both phases abundant in excess of the methods dissolution capacity. Leaching was performed with 1) hydroxylamine-HCl and 2) Na-dithionite as the reactive agent. Following Poulton & Canfield (2005) [1], the first dissolution is designed to selectively leach the most reactive Fe-phases, ferrihydrite and lepidocrocite, whereas the second dissolution is designed to leach goethite and hematite. Magnetite would then be dissolved in a third dissolution step with oxalic acid. First results show that the hydroxylamine-HCl method for ferrihydrite dissolves only insignificant amounts of goethite and hematite. However, magnetite-Fe constitutes about 10% of the total dissolved Fe. The Na-dithionite dissolved Fe from goethite-magnetite and hematite-magnetite mixtures contain about 30% of magnetite-Fe. We applied selective sequential leaching and Fe isotope analysis to fine-grained marine sediments from a depocenter in the North Sea, which contain abundant reactive Fe (oxyhydr)oxides and show evidence for Fe sulfide formation within the upper 10 cm. Fe isotopes of the hydroxylamine-HCl leach targeting ferrihydrite shows a downcore increase of !56Fe typical for sediments undergoing microbial reductive Fe dissolution, whereas Fe isotopes of the Na-dithionite leach (goethite and hematite) and oxalic acid leach (magnetite) are identical and show no downcore variation in !56Fe. This means, that only the most reactive Fe phases participate in the Fe redox cycle in this location. The similar isotopic composition of goethite + hematite and magnetite suggests a detrital source, which is not utilized possibly due to the abundant ferrihydrite and lepidocrocite present. [1] Poulton & Canfield (2005), Chemical Geology 214, 209– 221

Description: The glacier melt of the Western Antarctic Peninsula and its surrounding islands influences biogeochemical processes in the water column and the marine sediment by changing the flux of mineral particles and nutrients (e.g. Fe) into the ocean. Sediment and pore water samples were collected at King George Island (South Shetland Islands) to unravel how the vicinity of ice-covered and -uncovered terrestrial environment affects redox zonation and diagenetic processes in the coastal sediments. The post-depositional dissolution of Fe-minerals and the stable Fe isotope signatures of pore water and specific Fe minerals were of special interest since changing Fe supplies - as reactive particles via melting icebergs or meltwater streams or dissolved via diffusion from the sediment into the bottom water - might not only impact local biogeochemical cycles but most likely also impact productivity in the Southern Ocean. Sediment cores of up to 45 cm length were retrieved in Potter Cove, Marian Cove, and Maxwell Bay. In vicinity to the glaciers the sediments showed an extended redox zonation. The post-oxic zone with Fe2+ concentrations of up to 300 μM ranged from 1 to 25 cm depth. Most probably, microbial activity in sediments close to the glaciers is sluggish due to low input of organic matter (OM). More condensed redox zones prevailed in troughs where OM from terrestrial or marine sources accumulates and in vicinity to research stations. The upward directed diffusive Fe2+ fluxes as inferred from pore water profiles range between 0 and ~1050 μM m-2 d-1. However, the correlation to the intensity of diagenesis is not straightforward. Fe isotopes of specific minerals were used to assess the intensity of Fe cycling. With ongoing Fe-oxide dissolution, the residual Fe pool becomes enriched in 56Fe, whereas dissolved Fe and secondary Fe-oxides become enriched in 54Fe. Thus, easily reducible Fe oxides show lowest !56Fe values at the top of the sediment column. We suggest that the retreat of the glaciers indirectly results in higher OM fluxes to shelf areas fueling diagenetic processes/nutrient recycling.

Description: Diagenesis can have a major impact on sedimentary mineralogy. Primary magnetic mineral assemblages can be modified significantly by dissolution or by formation of new magnetic minerals during early or late diagenesis. At International Ocean Discovery Program Site C0023, which was drilled in the protothrust zone of the Nankai Trough during Expedition 370, offshore of Shikoku Island, Japan, non-steady state conditions have produced a complex sequence of magnetic overprints. Detailed rock magnetic measurements, which characterize magnetic mineral assemblages in terms of abundance, grain size, and composition, were conducted to assess magnetic mineral alteration and diagenetic overprinting. Four magnetic zones (MZs) are identified down-core from ∼200 to 1100 meters below sea floor based on rock magnetic variations. MZ 1 is a high magnetic intensity zone that contains ferrimagnetic greigite, which formed at shallow depths and is preserved because of rapid sedimentation. MZs 2 and 4 are low magnetic intensity zones with fewer magnetic minerals, mainly coarse-grained (titano-)magnetite and hematite. This magnetic mineral assemblage is a remnant of a more complex assemblage that was altered diagenetically a few million years after deposition when the site entered the Nankai Trough. MZ 3 is a high magnetic intensity zone between MZs 2 and 4. It contains authigenic single-domain magnetic particles that probably formed from fluids that circulated through faults in the accretionary prism. Varying sediment supply and organic matter input through time, burial temperature, and tectonic fluid circulation are the primary drivers of magnetic mineral assemblage variations.

Description: Rapid and profound climatic and environmental changes have been predicted for the Antarctic Peninsula with so far unknown impact on the biogeochemistry of the continental shelves. In this study, we investigate benthic carbon sedimentation, remineralization and iron cycling using sediment cores retrieved on a 400 mile transect with contrasting sea ice conditions along the eastern shelf of the Antarctic Peninsula. Sediments at comparable water depths of 330-450 m showed sedimentation and remineralization rates of organic carbon, ranging from 2.5-13 and 1.8-7.2 mmol C m-2 d-1, respectively. Both rates were positively correlated with the occurrence of marginal sea ice conditions (5-35% ice cover) along the transect, suggesting a favorable influence of the corresponding light regime and water column stratification on algae growth and sedimentation rates. From south to north, the burial efficiency of organic carbon decreased from 58% to 27%, while bottom water temperatures increased from -1.9 to -0.1 °C. Net iron reduction rates, as estimated from pore-water profiles of dissolved iron, were significantly correlated with carbon degradation rates and contributed 0.7-1.2% to the total organic carbon remineralization. Tightly coupled phosphate-iron recycling was indicated by significant covariation of dissolved iron and phosphate concentrations, which almost consistently exhibited P/Fe flux ratios of 0.26. Iron efflux into bottom waters of 0.6-4.5 µmol Fe m-2 d-1 was estimated from an empirical model. Despite the deep shelf waters, a clear bentho-pelagic coupling is indicated, shaped by the extent and duration of marginal sea ice conditions during summer, and likely to be affected by future climate change.