Description: In order to analyse differences in concentration, speciation and total mobility of arsenic two different locations were studied near the Helgoland Mud Area, North Sea. The first location is characterised by natural sedimentation, the second by deposited sediments dredged from the port of Hamburg. Porewater as well as sediment profiles were analysed with respect to arsenic compounds (As (III) and total As) and major redox species as total and reactive manganese and iron. The sediment samples were handled under inert atmosphere before and during extraction by water, phosphate, hydrochloric acid and aqua regia. Total element contents in porewater and leachable extracts of sediment fractions were analysed. The results show a strong redox coupling of arsenic with manganese and iron. Oxidized arsenic seems to adsorb to manganese- and iron-oxyhydroxides in surface sediments. In contrast to the solid samples, the pore water data shows a release of As (III) into porewater when manganese- and ironoxyhydroxides are reduced in the upper part of the cores. Also a remobilisation of As (V) occurs. Downward diffusing arsenic can be fixed by carbonate below the zone of manganese and iron reduction. In the anoxic parts of the sediments As (III) and As (V) are released and could be fixed at authigenic iron sulphide or arsenic sulphides formation. A sulfidic precipitation of arsenic in iron-dominated systems is limited by the occurrence of HS-. Total solid-phase contents in leachable extracts of sediment fractions of the natural area show significant higher arsenic concentrations than the core of the anthropogenic dumping area. This is due to the higher fines content of the Helgoland mud area. Higher total porewater contents of iron and arsenic in the core of the anthropogenic dumping area thus due to higher turnover rates of organic matter by iron reduction. Higher concentrations of arsenic may be due to a higher availability of iron in the dumped sediments.

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: Sulfate is the dominant terminal electron acceptor in marine sediments. Sulfate reduction proceeds under anoxic conditions and is supported by a variety of electron donors (e.g. hydrogen, acetate, methane, propane, and butane), most of which are supplied by the decomposition of sedimentary organic matter. Consequently, a combination of primary productivity and water column depth is often thought to control sulfate reduction throughout most of the ocean’s seafloor [1, 2]. However, global models of sulfate reduction do not resolve the many different physical and ecological parameters that are encountered on a global scale, and that ultimately play a major role in driving local and regional sulfate reduction rates. We sought to better determine sulfate reduction rates on a global scale, irrespective of region or location by 1) including sulfate profiles from diverse settings and 2) compiling multiple geochemical parameters that are relevant to sulfate reduction and can help discern the magnitude of sulfate reduction rates. All available sulfate concentration profiles from DSDP/ODP/IODP (to Exp. 312) and additionally those in the database Pangaea (www.pangaea.de) were compiled reaching a total 〉600 nonrepetitive concentration profiles. Basic metadata describing the cores was included, such as water depth and distance to shore. Water column data such as minimum percent O2 saturation, bottom water O2, NO3 -, PO4 3-, and concentrations of surface water chlorophyll a and POC [3, 4] were included as additional variables that describe the biogeochemical setting of the cores. All compiled data and concentration profiles were applied to a training algorithm to estimate global sulfate reduction rates. The result was the most precise depiction of global sulfate reduction rates at the highest resolution to date. Our model serves as a platform for the examination of biogeochemical processes on the global scale and lets us predict energetic constraints for microbial metabolism in the subseafloor. [1] Canfield (1991) AJOS 291, 177-188. [2] Middelburg et al. (1997) DSR 44, 327-344. [3] Levitus & Boyer (1994) NOAA Atlas NESDIS [4] NASA, Aqua-MODIS

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.