Total dissolved organic carbon and total dissolved nitrogen in sediment pore water of the central Arctic Ocean collected during POLARSTERN cruise ARK-XXVII/3 from August-September 2012

During the RV Polarstern cruise ARK-XXVII/3 to the Arctic Ocean in summer 2012, when sea ice declined to a record minimum bottom, water and sediment pore water samples were collected with a TV-guided multicorer at stations in the Nansen and Amundsen basin. 50 ml sediment pore water samples were collected from 0-1, 1-5 and 5-10 cm sediment depths from up to 4 parallel sediment cores at each station. Additionally, overlying bottom waters were carefully collected from undisturbed sediment cores. Acidified pore water samples (pH2) were used for analysis of DOC and TDN concentrations. The measurements were performed by hand injection via catalytic oxidation at high temperature on a TOC-V Shimadzu instrument.

(Table 1) Pore water halogen concentrations in ODP Holes 169-1033B and 169-1034B

The entire suite of halogens was measured in the pore fluids of Hole 1033B and 1034B from Saanich Inlet: ODP Leg 169S. The fast sedimentation rates and large amount of organic carbon burial coupled with anoxia of the overlying waters promotes an advanced stage of diagenesis within the sediment column. Chloride interstitial water profiles suggest salinity variations within the waters of Saanich Inlet. Concentration profiles for iodide and bromide support the argument that they are produced through the degradation of organic matter. Although the concentration increases in I- and Br- indicate that these halides are not regenerated in similar proportions to marine organic matter, it appears that iodide and bromide are regenerated to similar degrees within the sediment column and in similar proportions to the sediment halide concentrations. Fluoride porewater values show a complicated pattern, most likely caused by secondary reactions involving complexation with Mg2+, carbonate fluorapatite precipitation, carbonate mineral diagenesis, and/or uptake into alumino-silicate minerals.

(Table 1) Minor and trace element concentrations in interstitial waters from ODP Leg 166 sites

Concentrations of minor and trace elements (Li, Rb, Sr, Ba, Fe, and Mn) in interstitial water (IW) were found in samples collected during Ocean Drilling Program (ODP) Leg 166 from Sites 1005, 1006, and 1007 on the western flank of the Great Bahama Bank (GBB). Concentrations of Li range from near-seawater values immediately below the sediment/water interface to a maximum of 250 µM deep in Site 1007. Concentrations determined during shore-based studies are substantially lower than the shipboard data presented in the Leg 166 Initial Reports volume (range of 28-439 µM) because of broad-band interferences from high dissolved Sr concentrations in the shipboard analyses. Rubidium concentrations of 1.3-1.7 µM were measured in IW from Site 1006 when salinity was less than 40 psu. A maximum of 2.5 µM is reached downhole at a salinity of 50 psu. Shipboard and shore-based concentrations of Sr2+ are in excellent agreement and vary from 0.15 mM near the sediment water interface to 6.8 mM at depth. The latter represent the highest dissolved Sr2+ concentrations observed to date in sediments cored during the Deep Sea Drilling Project (DSDP) or ODP. Concentrations of Ba2+ span three orders of magnitude (0.1-227µM). Concentrations of Fe (<0.1-14 µM) and Mn (0.1-2 µM) exhibit substantially greater fluctuations than other constituents. The concentrations of minor and trace metals in pore fluids from the GBB transect sites are mediated principally by changes in pore-water properties resulting from early diagenesis of carbonates associated with microbial degradation of organic matter, and by the abundance of detrital materials that serve as a source of these elements. Downcore variations in the abundance of detrital matter reflect differences in carbonate production during various sea-level stands and are more evident at the more proximal Site 1005 than at the more pelagic Site 1006. The more continuous delivery of detrital matter deep in Site 1007 and throughout all of Site 1006 is reflected in a greater propensity to provide trace elements to solution. Concentrations of dissolved Li+ derive principally from (1) release during dissolution of biogenic carbonates and subsequent exclusion during recrystallization and (2) release from partial dissolution of Li-bearing detrital phases, especially ion-exchange reactions with clay minerals. A third but potentially less important source of Li+ is a high-salinity brine hypothesized to exist in Jurassic age (unsampled) sediments underlying those sampled during Leg 166. The source of dissolved Sr2+ is almost exclusively biogenic carbonate, particularly aragonite. Concentrations of dissolved Sr2+ and Ba2+ are mediated by the solubility of their sulfates. Barite and detrital minerals appear to be the more important source of dissolved Ba2+. Concentrations of Fe and Mn2+ in anoxic pore fluids are mediated by the relative insolubility of pyrite and incorporation into diagenetic carbonates. The principal sources of these elements are easily reduced Fe-Mn-rich phases including Fe-rich clays found in lateritic soils and aoelian dust.

Chemical and isotopic compositions of pore fluids from ODP Sites 169-1034 and 169-1037

We have analysed the concentrations of Li, K, Rb, Cs, and B, and the isotopic ratios of Li and B of a suite of pore fluids recovered from ODP Sites 1037 (Leg 169; Escanaba Trough) and 1034 (Leg 169S; Saanich Inlet). In addition, we have analysed dissolved K, Rb, and Cs concentrations for estuarine mixing of the Ganges-Brahmaputra river system. Together, these data sets have been used to assess the role of sediments in the marine geochemical cycles of the alkali elements and boron. Uptake onto clay minerals during estuarine mixing removes 20-30% of the riverine input of dissolved Cs and Rb to the oceans. Prior to this study, the only other recognised sink of Rb and Cs was uptake during low-temperature alteration of the oceanic crust. Even with this additional sink there is an excess of inputs over outputs in their modern oceanic mass balance. Pore fluid data show that Li and Rb are transferred into marine sediments during early diagenesis. However, modeling of the Li isotope systematics of the pore fluids from Site 1037 shows that seawater Li taken up during marine sedimentation can be readily returned to solution in the presence of less hydrated cations, such as NH4+. This process also appears to result in high concentrations of pore fluid Cs (relative to local seawater) due to expulsion of adsorbed Cs from cation exchange sites. Flux calculations based on pore fluid data for a series of ODP sites indicate that early diagenesis of clay sediments removes around 8% of the modern riverine input of dissolved Li. Although NH4+-rich fluids do result in a flux of Cs to the oceans, on the global scale this input only augments the modern riverine Cs flux by ~3%. Nevertheless, this may have implications for the fate of radioactive Cs in the natural environment and waste repositories.

Sediment and pore water data of five cores from the continental slope off Uruguay

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 (SO4**2-) profile at 2.8 m depth. A sharp sedimentological contact at 2.43 m coincides with an abrupt downward increase in shear strength from approx. 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 SO4**2- profile approx. 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 SO4**2- the age of the most recent MTD is estimated to be <30 years. The mass movement was possibly related to an earthquake in 1988 (approx. 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.

Sulfate and methane concentrations measured in pore water of sediment core GeoB13809-1 and GeoB13849-1

Several previous studies have shown that submarine mass-movements can profoundly impact the shape of pore water profiles. Therefore, pore water geochemistry and diffusion models were proposed as tools for identifying and dating recent (max. several thousands of years old) mass-transport deposits (MTDs). In particular, sulfate profiles evidentially indicate transient pore water conditions generated by submarine landslides. After mass-movements that result in the deposition of sediment packages with distinct pore water signatures, the sulfate profiles can be kink-shaped and evolve into the concave and linear shape with time due to molecular diffusion. Here we present data from the RV METEOR cruise M78/3 along the continental margin off Uruguay and Argentina. Sulfate profiles of 15 gravity cores are compared with the respective acoustic facies recorded by a sediment echosounder system. Our results show that in this very dynamic depositional setting, non-steady state profiles occur often, but are not exclusively associated with mass-movements. Three sites that show acoustic indications for recent MTDs are presented in detail. Where recent MTDs are identified, a geochemical transport/reaction model is used to estimate the time that has elapsed since the perturbation of the pore water system and, thus, the timing of the MTD emplacement. We conclude that geochemical analyses are a powerful complementary tool in the identification of recent MTDs and provide a simple and accurate way of dating such deposits.

Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.