ALBERT

Description: High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (View the MathML sourceSO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate–methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, ‘relict’ barite fronts would only be preserved for a few thousands of years, if at all.

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 Corg 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: Rare earth elements and yttrium (REY) are often used as proxies for (paleo)environmental conditions and for the reconstruction of element sources and transport pathways. Many geological systems are well described with respect to the behavior of REY but deep-sea sediments with their manifold processes impacting the sediment during early diagenesis leave some questions about the origin and development of the shale-normalized REY (REYSN) patterns unanswered. Here we report REY data for sediment solid phase and pore water from the upper 10 m of deep-sea sediments from the Clarion Clipperton Zone (CCZ) in the central equatorial Pacific. The solid-phase REY profiles show highest concentrations at depth below 5–8 m. The REYSN patterns show an enrichment in middle REY (MREY) (LaSN/GdSN between 0.35 and 0.60; GdSN/YbSN between 1.19 and 1.47) and either no or negative CeSN and YSN anomalies (i.e. chondritic to sub-chondritic Y/Ho ratios between 24.7 and 28.7). Based on correlation analyses of bulk sediment element concentrations and sequential extractions, we suggest that a Ca phosphate phase controls the distribution and the patterns of REY in these silty clay pelagic sediments rich in siliceous ooze. The MREY enrichment develops at the sediment-water interface and intensifies systematically with depth. The negative CeSN anomaly intensifies with depth possibly because Ce is mostly bound to Mn- and Fe-(oxyhydr)oxides. Therefore, Ce concentrations remain relatively constant throughout the sediment core, while its trivalent REY neighbors are mostly hosted by the Ca phosphate phase that continuously incorporates REY from ambient pore waters. The non-redox-sensitive trivalent REY concentrations increase with depth, producing or enhancing a negative CeSN anomaly through coupled substitution of REY3+ and Na+ for Ca2+. The solid-phase REYSN pattern is therefore determined by the pore-water REYSN pattern and not suitable for paleoceanographic interpretation. The similarity of the pore-water and solid-phase REYSN patterns suggests, however, that only minor fractionation occurs during REY incorporation into the Ca phosphate crystal structure.

Description: Numerous studies have provided compelling evidence that the Pacific Ocean has experienced substantial glacial/interglacial changes in bottom-water oxygenation associated with enhanced carbon dioxide storage in the glacial deep ocean. Under postulated low glacial bottom-water oxygen concentrations (O), redox zonation, biogeochemical processes and element fluxes in the sediments must have been distinctively different during the last glacial period (LGP) compared to current well-oxygenated conditions. In this study, we have investigated six sites situated in various European contract areas for the exploration of polymetallic nodules within the Clarion-Clipperton Zone (CCZ) in the NE Pacific and one site located in a protected Area of Particular Environmental Interest (APEI3) north of the CCZ. We found bulk sediment Mn maxima of up to 1 wt% in the upper oxic 10 cm of the sediments at all sites except for the APEI3 site. The application of a combined leaching protocol for the extraction of sedimentary Mn and Fe minerals revealed that mobilizable Mn(IV) represents the dominant Mn(oxyhydr)oxide phase with more than 70% of bulk solid-phase Mn. Steady state transport-reaction modeling showed that at postulated glacial O of 35 μM, the oxic zone in the sediments was much more compressed than today where upward diffusing pore-water Mn2+ was oxidized and precipitated as authigenic Mn(IV) at the oxic-suboxic redox boundary in the upper 5 cm of the sediments. Transient transport-reaction modeling demonstrated that with increasing O during the last glacial termination to current levels of ∼ 150 μM, (1) the oxic-suboxic redox boundary migrated deeper into the sediments and (2) the authigenic Mn(IV) peak was continuously mixed into subsequently deposited sediments by bioturbation causing the observed mobilizable Mn(IV) enrichment in the surface sediments. Such a distinct mobilizable Mn(IV) maximum was not found in the surface sediments of the APEI3 site, which indicates that the oxic zone was not as condensed during the LGP at this site due to two- to threefold lower organic carbon burial rates. Leaching data for sedimentary Fe minerals suggest that Fe(III) has not been diagenetically redistributed during the LGP at any of the investigated sites. Our results demonstrate that the basin-wide deoxygenation in the NE Pacific during the LGP was associated with (1) a much more compressed oxic zone at sites with carbon burial fluxes higher than 1.5 mg Corg m−2 d−1, (2) the authigenic formation of a sub-surface mobilizable Mn(IV) maximum in the upper 5 cm of the sediments and (3) a possibly intensified suboxic-diagenetic growth of polymetallic nodules. As our study provides evidence that authigenic Mn(IV) precipitated in the surface sediments under postulated low glacial O, it contributes to resolving a long-standing controversy concerning the origin of widely observed Mn-rich layers in glacial/deglacial deep-sea sediments.

Description: Highlights • Release of dissolved Sr2+ with low 87Sr/86Sr, as well as Ca2+ and Ba2+ suggests ongoing volcanic ash alteration. • A concurrent increase in Fe2+ and a depletion of CH4 with a decrease in C of CH4 and DIC suggest Fe-AOM. • We for the first time document the potential linkage between ash alteration and methane oxidation via Fe-AOM. • The rate of Fe-AOM is estimated to be ∼0.4 μmol cm−2 yr−1, equivalent to ∼12% of total CH4 removal. Abstract We present geochemical data collected from volcanic ash-bearing sediments on the upper slope of the northern Hikurangi margin during the RV SONNE SO247 expedition in 2016. Gravity coring and seafloor drilling with the MARUM-MeBo200 allowed for collection of sediments down to 105 meters below seafloor (mbsf). Release of dissolved Sr2+ with isotopic composition enriched in 86Sr (87Sr/86Sr minimum = 0.708461 at 83.5 mbsf) is indicative of ash alteration. This reaction releases other cations in the 30-70 mbsf depth interval as reflected by maxima in pore-water Ca2+ and Ba2+ concentrations. In addition, we posit that Fe(III) in volcanogenic glass serves as an electron acceptor for methane oxidation, a reaction that releases Fe2+ measured in the pore fluids to a maximum concentration of 184 μM. Several lines of evidence support our proposed coupling of ash alteration with Fe-mediated anaerobic oxidation of methane (Fe-AOM) beneath the sulfate-methane transition (SMT), which lies at ∼7 mbsf at this site. In the ∼30-70 mbsf interval, we observe a concurrent increase in Fe2+ and a depletion of CH4 with a well-defined decrease in C-CH4 values indicative of microbial fractionation of carbon. The negative excursions in C values of both DIC and CH4 are similar to that observed by sulfate-driven AOM at low SO concentrations, and can only be explained by the microbially-mediated carbon isotope equilibration between CH4 and DIC. Mass balance considerations reveal that the iron cycled through the coupled ash alteration and AOM reactions is consumed as authigenic Fe-bearing minerals. This iron sink term derived from the mass balance is consistent with the amount of iron present as carbonate minerals, as estimated from sequential extraction analyses. Using a numerical modeling approach we estimate the rate of Fe-AOM to be on the order of 0.4 μmol cm−2 yr−1, which accounts for ∼12% of total CH4 removal in the sediments. Although not without uncertainties, the results presented reveal that Fe-AOM in ash-bearing sediments is significantly lower than the sulfate-driven CH4 consumption, which at this site is 3.0 μmol cm−2 yr−1. We highlight that Fe(III) in ash can potentially serve as an electron acceptor for methane oxidation in sulfate-depleted settings. This is relevant to our understanding of C-Fe cycling in the methanic zone that typically underlies the SMT and could be important in supporting the deep biosphere.