Description: Assessing frequency and extent of mass movement at continental margins is crucial to evaluate risks for offshore constructions and coastal areas. A multidisciplinary approach including geophysical, sedimentological, geotechnical, and geochemical methods was applied to investigate multistage mass transport deposits (MTDs) off Uruguay, on top of which no surficial hemipelagic drape was detected based on echosounder data. Nonsteady state pore water conditions are evidenced by a distinct gradient change in the sulfate (SO42−) profile at 2.8 m depth. A sharp sedimentological contact at 2.43 m coincides with an abrupt downward increase in shear strength from ∼10 to 〉20 kPa. This boundary is interpreted as a paleosurface (and top of an older MTD) that has recently been covered by a sediment package during a younger landslide event. This youngest MTD supposedly originated from an upslope position and carried its initial pore water signature downward. The kink in the SO42− profile ∼35 cm below the sedimentological and geotechnical contact indicates that bioirrigation affected the paleosurface before deposition of the youngest MTD. Based on modeling of the diffusive re-equilibration of SO42− the age of the most recent MTD is estimated to be 〈30 years. The mass movement was possibly related to an earthquake in 1988 (∼70 km southwest of the core location). Probabilistic slope stability back analysis of general landslide structures in the study area reveals that slope failure initiation requires additional ground accelerations. Therefore, we consider the earthquake as a reasonable trigger if additional weakening processes (e.g., erosion by previous retrogressive failure events or excess pore pressures) preconditioned the slope for failure. Our study reveals the necessity of multidisciplinary approaches to accurately recognize and date recent slope failures in complex settings such as the investigated area.

Description: The occurrence of gas hydrates at submarine mud volcanoes (MVs) located within the gas hydrate stability zone (GHSZ) is controlled by upward fluid and heat flux associated with MV activity. Determining the spatial distribution of gas hydrates at MVs is crucial to evaluate their sensitivity to known episodic changes in volcanic activity. We determined the hydrocarbon inventory and spatial distribution of hydrates at an individual MV structure. The Hakon Mosby Mud Volcano (HMMV), located at 1,250 m water depth on the Barents Sea slope, was investigated by combined pressure core sampling, heat flow measurements, and pore water chemical analysis. Quantitative pressure core degassing revealed gas-sediment ratios between 3.1 and 25.7, corresponding to hydrate concentrations of up to 21.3% of the pore volume. Hydrocarbon compositions and physicochemical conditions imply that gas hydrates incipiently crystallize as structure I hydrate, with a dissociation temperature of around 13.8 degrees C at this water depth. Based on numerous in situ measurements of the geothermal gradient in the seabed, pore water sulfate profiles and microbathymetric data, we show that the thickness of the GHSZ increases from less than 1 m at the warm center to around 47 m in the outer parts of the HMMV. We estimate the total mass of hydrate-bound methane stored at the HMMV to be about 102.5 kt, of which 2.8 kt are located within the morphological Unit I around the center and thus are likely to be dissociated in the course of a large eruption.

Description: The development of stable barium (Ba) isotope measurements provides a novel tool to investigate the geochemical cycling of Ba in the ocean and its sediments. In sediment pore waters, gradients of dissolved Ba concentrations result from various diagenetic processes. The distribution and fractionation of Ba isotopes in the pore waters are expected to further improve our understanding of these early diagenetic control mechanisms. Here, we present pore water profiles of dissolved stable Ba isotopic signatures (δ138Bapw) from shallow water sediments covering the entire Pearl River Estuary (PRE) in Southern China. We find pronounced depth-dependent Ba isotope variations generally showing a shift from heavy to light δ138Bapw signatures from the sediment surface down to 15 cm depth. These gradients are well reproduced by a diffusion-reaction model, which generates an apparent fractionation factor (138ε) of −0.60 ± 0.10‰ pointing to preferential removal of low-mass Ba isotopes from the pore water during solution-solid phase interactions. Consequently, the combined diagenetic processes induce the highest δ138Bapw values of +0.5 to +0.7‰ in the pore waters of the topmost sediment layer. Although the detrital fraction dominates the Ba content in the PRE surface sediments, the determined gradients of pore water Ba isotopes, together with concentration variations of Ba and other redox-sensitive elements such as manganese (Mn), show that non-detrital excess Ba carriers including Mn oxides and authigenic barite clearly affect the post-depositional Ba dynamics. Stable Ba isotopes are thus a potentially powerful tracer of Ba geochemistry during early sediment diagenesis in estuarine depositional environments. Key Points We present a data set of dissolved stable Ba isotopic compositions in surface sediment pore waters of a large river estuary Pore water Ba isotope values generally decrease with increasing sediment depth, reflecting post-depositional Ba isotope fractionation A diffusion-reaction model predicts the distribution and fractionation of stable Ba isotopes in the sediment pore waters well

Description: Iron (Fe) fluxes from reducing sediments and subglacial environments are potential sources of bioavailable Fe into the Southern Ocean. Stable Fe isotopes (δ56Fe ) are considered a proxy for Fe sources and reaction pathways, 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 present δ56Fe data from pore waters and sequentially extracted sedimentary Fe phases of two contrasting sites in Potter Cove (King George Island, Antarctic Peninsula), a bay that is affected by fast glacier retreat. Sediments close to the glacier front contain more easily reducible Fe oxides and pyrite and show a broader ferruginous zone, compared to sediments close to the icefree coast, where surficial oxic meltwater streams discharge into the bay. Pyrite in sediments close to the glacier front predominantly derives from eroded bedrock. For the high amount of easily reducible Fe oxides proximal to the glacier we suggest mainly subglacial sources, where Fe liberation from comminuted material beneath the glacier is coupled to biogeochemical weathering processes (likely pyrite oxidation or dissimilatory iron reduction, DIR). Our strongest argument for a subglacial source of the highly reactive Fe pool in sediments close to the glacier front is its predominantly negative δ56Fe signature that remains constant over the whole ferruginous zone. This implies in situ DIR does not significantly alter the stable Fe isotope composition of the accumulated Fe oxides. The nonetheless overall light δ56Fe signature of easily reducible Fe oxides suggests pre-depositional microbial cycling as it occurs in potentially anoxic subglacial environments. The strongest 56Fe-depletion in pore water and most reactive Fe oxides was observed in sediments influenced by oxic meltwater discharge. The respective site showed a condensed redox zonation and a pore water δ56Fe profile typical for in-situ Fe cycling. We demonstrate that the potential of pore water δ56Fe as a proxy for benthic Fe fluxes is not straight-forward due to its large variability in marine shelf sediments at small spatial scales (- 2.4‰ at the site proximal to oxic meltwater discharge vs. -0.9‰ at the site proximal to the marine glacier terminus, both at 2 cm sediment depth). The controlling factors are multifold and include the amount and reactivity of reducible Fe oxides and organic matter, the isotopic composition of the primary and secondary ferric substrates, sedimentation rates, and physical reworking (bioturbation, ice scraping). The application of δ56Fe geochemistry may prove valuable in investigating biogeochemical weathering and Fe cycling in subglacial environments. This requires, however (similarly to the use of δ56Fe for the quantification of benthic fluxes), that the spatial and temporal variability of the isotopic endmember is known and accounted for. Since geochemical data from subglacial environments are very limited, further studies are needed in order to sufficiently assess Fe cycling and fractionation at glacier beds and the composition of discharges from those areas.

Description: The manganese nodule belt within the Clarion and Clipperton Fracture Zones (CCZ) in the abyssal NE Pacific Ocean is characterized by numerous seamounts, low organic matter (OM) depositional fluxes and meter-scale oxygen penetration depths (OPD) into the sediment. The region hosts contract areas for the exploration of polymetallic nodules and Areas of Particular Environmental Interest (APEI) as protected areas. In order to assess the impact of potential mining on these deep-sea sediments and ecosystems, a thorough determination of the natural spatial variability of depositional and geochemical conditions as well as biogeochemical processes and element fluxes in the different exploration areas is required. Here, we present a comparative study on (1) sedimentation rates and bioturbation depths, (2) redox zonation of the sediments and element fluxes as well as (3) rates and pathways of biogeochemical reactions at six sites in the eastern CCZ. The sites are located in four European contract areas and in the APEI3. Our results demonstrate that the natural spatial variability of depositional and (bio)geochemical conditions in this deep-sea sedimentary environment is much larger than previously thought. We found that the OPD varies between 1 and 4.5 m, while the sediments at two sites are oxic throughout the sampled interval (7.5 m depth). Below the OPD, manganese and nitrate reduction occur concurrently in the suboxic zone with pore-water Mn2+ concentrations of up to 25 µM. The thickness of the suboxic zone extends over depth intervals of less than 3 m to more than 8 m. Our data and the applied transport-reaction model suggest that the extension of the oxic and suboxic zones is ultimately determined by the (1) low flux of particulate organic carbon (POC) of 1–2 mg Corg m−2 d−1 to the seafloor, (2) low sedimentation rates between 0.2 and 1.15 cm kyr−1 and (3) oxidation of pore-water Mn2+ at depth. The diagenetic model reveals that aerobic respiration is the main biogeochemical process driving OM degradation. Due to very low POC fluxes of 1 mg m−2 d−1 to the seafloor at the site investigated in the protected APEI3 area, respiration rates are twofold lower than at the other study sites. Thus, the APEI3 site does not represent the (bio)geochemical conditions that prevail in the other investigated sites located in the European contract areas. Lateral variations in surface water productivity are generally reflected in the POC fluxes to the seafloor across the various areas but deviate from this trend at two of the study sites. We suggest that the observed spatial variations in depositional and (bio)geochemical conditions result from differences in the degree of degradation of OM in the water column and heterogeneous sedimentation patterns caused by the interaction of bottom water currents with seafloor topography.

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