Beschreibung: 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 CH4with a well-defined decrease in δ13C-CH4values indicative of microbial fractionation of carbon. The negative excursions in δ13C values of both DIC and CH4are similar to that observed by sulfate-driven AOM at low SO2−4concentrations, and can only be explained by the microbially-mediated carbon isotope equilibration between CH4and 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 0.4μmol cm−2yr−1, which accounts for ∼12% of total CH4removal 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 CH4consumption, which at this site is 3.0μmol cm−2yr−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.

Beschreibung: Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34S values of pyrite (δ34Spy) have been used to trace the AOM-related processes. However, the detailed mechanism for this phenomenon is not well understood. We propose that the characteristics of δ34Spy were mainly controlled by the competition between sulfate reduction and sulfate supply, as well as the redox condition. To test this hypothesis, we investigated Sr/Ca and Mg/Ca ratios, trace element compositions, pyrite contents and sulfur isotopic compositions in seep carbonates from Site F and Haima in the northern South China Sea. Calcite and aragonite contents were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34Spy values compared to calcites. The Mo contents show a good correlation with pyrite contents in calcites and aragonites, and the slope in aragonites is larger than that in calcites. This relationship indicates that the aragonite precipitated in a relatively open system with higher Mo availability. Thus, we conclude that sulfides with low δ34S values formed at high supply of sulfate under the relatively open system with respect to diffusive replenishment of sulfate, where the carbonate precipitation occurred close to the seafloor due to a strong methane flux. Under vigorous methane flux simultaneously, the high potential of less anoxic conditions, which could limit the additional pyrite accumulation and/or favor the microbial disproportionation, could also be the cause of the low δ34Spy, as supported by samples from the Haima sites. Evidence for this assumption is based on the occurrence of bivalve shells and less enrichment in As and Sb. Conversely, the positive δ34Spy values result from near to complete exhaustion of dissolve sulfate via AOM within a deeper sulfate-methane transition zone, where Mo is less available. The combination of a detailed elemental study of authigenic carbonates with sulfur isotopic composition of sulfide minerals in carbonates is a promising tool for reconstructing the dynamics of seep intensities at modern and, potentially, geological seep sites.

Beschreibung: Sulfate-driven anaerobic oxidation of methane (SD-AOM) plays a critical role in regulating the global methane budget. Determination of the diagnostic triple isotope exponent 33 e (= ln33 a/ln34 a) for SDAOM can help to identify and quantify microbial sulfate reduction via SD-AOM in the environment. The history of Earth's surface red ox conditions can also be examined through the measurement of triple sulfur isotope compositions in sedimentary rocks. Due to difficulties in both culturing anaerobic methanotrophs and sampling pore-water sulfate in SD-AOM-dominated environments. however. the 33 e values for the processes of SD-AOM have not been constrained. We propose that a set of modern cold-seep associated barite samples with low ll8 18 0j !l834S values bear a record of residual pore-water sulfate during SDAOM. and therefore the triple sulfur isotope composition of these barites can be used to deduce 33 e values. We applied a 1-D diagenetic reaction-transport model to fit !l 33S and 8134S results from modern cold seep barites collected from five sites in the Gulf of Mexico. Based on revealed negative correlations (R2 = 0.77) between !l33 S and 8134S values we calculated an upper-limit 33 e value of 0.5100 to 0.5112 (±0.0005) given a 1000ln34 a value of -30%0 to -10%0. This 33 e value is distinctively lower than that of organoclastic sulfate reduction ( OSR) in marine environments where the diagnostic isotope fractionation ( 1000 ln34 a) is typically more negative than that of SD-AOM. In addition. cold seep barite data display a negative !l 33 S-81 34S correlation whereas pore-water sulfates of all OSR-dominated settings show a positive one. Therefore. the diagnostic triple-sulfur isotope exponent and associated negative !l 33S-8134S correlation may allow for the identification of SD-AOM in sedimentary records.

Beschreibung: Highlights • Elemental and radiocarbon analysis of southern Mariana Trench (SMT) sediments since 30 ka. • Shift to more reducing (suboxic) deep waters during the Last Glacial Maximum (LGM). • Blooms of giant diatom Ethmodiscus rex formed laminated diatom mats (LDMs) during LGM. •Redox changes were due to increased primary productivity induced by enhanced Asian dust inputs. • Biogenic and authigenic apatite are the main carriers of rare earth elements (REEs) in SMT sediments. Abstract: The modern southern Mariana Trench is characterized by oligotrophic surface waters, resulting in low primary productivity and well-oxygenated bottom waters. This study investigates changes in the redox conditions of bottom waters in the southern Mariana Trench during the Last Glacial Maximum (LGM) and their potential causes. We measured major, trace, and rare earth elements (REE) in three gravity cores (GC03, GC04, and GC05) and one box core (BC11) retrieved from the southern Challenger Deep at water depths from 5289 to 7118 m. The upper sediment layers of both GC05 and BC11 are dominated by valve fragments of the giant diatom Ethmodiscus rex, forming laminated diatom mats (LDMs). 14C-AMS dates of bulk organic matter show that the LDMs accumulated between 18.4 and 21.8 kyr B.P., corresponding to the LGM. Modest enrichments of U and Mo along with weak or absent Ce anomalies in the LDM point to suboxic conditions during the LGM. In contrast, non-LDM samples exhibit little to no enrichment of redox-sensitive elements as well as negative Ce anomalies, indicating deposition under oxic bottom-water conditions. The Ce anomalies are considered valid proxies for bottom-water redox conditions because REE signatures were acquired in the early diagenetic environment, as indicated by strong P-REE correlations and middle-REE enrichment associated with early diagenetic cycling of Fe-Mn oxyhydroxides in the sediment column followed by capture of the REE signal by biogenic and/or authigenic apatite. We postulate that the more reducing bottom-water conditions during the LGM were linked to increased primary productivity induced by enhanced Asian dust input. As shown in earlier studies, the increased primary productivity associated with Ethmodiscus rex blooms in the eastern Philippine Sea played a significant role in capturing atmospheric CO2 during the LGM. Consequently, the magnitude of atmospheric CO2 sequestration by giant diatom blooms during the LGM may have been greater than previously envisaged.

Beschreibung: Carbon cycling and fluid seepage in marine sediments over the late Quaternary were investigated at a now-extinct pockmark located in a mega-pockmark field in the SW Xisha Uplift (NW South China Sea). Measured particulate organic carbon (POC) content, and porewater sulfate (SO4 2-), dissolved inorganic carbon (DIC) concentrations and δ34S-SO4 2- distributions were used to constrain a non-steady-state reaction-transport model and quantify POC mineralization rates as well as estimate the time when fluid flow ceased at the investigated pockmark. An increase in POC content and δ34S-SO4 2- and a decrease in sulfate concentrations in the upper ca. 2m at the pockmark and a reference core implied an increase in the flux and reactivity of organic matter during the early Holocene around 10kyrB. P. caused by enhanced primary productivity during the strengthened southwestern summer monsoon. These features were simulated with the model assuming a Holocene increase in POC flux and reactivity. Subsequently, starting from an initial condition reminiscent of a modern active cold seep (Hydrate Ridge), hindcast simulations showed that fluid seepage at the pockmark ceased ca. 39kyr ago. This corresponds to a relative sea level high-stand, which is believed to be associated with gas hydrate stabilization. The non-steady-state model presented in this contribution can also be used to constrain the time when fluid seepage ceased at other presently extinct cold seeps when suitable sediment and porewater data are available.

Beschreibung: 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.

Beschreibung: Fluid flow patterns at cold seeps provide insights into the mechanism and influence of methane emission into the ocean, which is critical in its environmental impact assessment. Here, we report pore fluid compositions of three ~8 m long piston cores (QDN-14A, QDN-14B and R1) collected from the newly-discovered active Haima cold seeps on the northwestern slope of the South China Sea. Reaction-transport models were further applied to quantify related biogeochemical processes and to reveal the patterns of fluid flow. Extremely low δ13C values (〈 -52‰) of dissolved inorganic carbon (DIC) near the sulfate-methane transition in the three cores suggest that anaerobic oxidation of methane is the predominant biogeochemical process. The presence of small pieces of gas hydrates along with negative anomalies of porewater chloride and sodium concentrations reflects gas hydrate dissociation. Nearly invariable concentrations of sulfate, DIC, and calcium on a meter-scale were observed in the uppermost part of the sediment cores QDN-14A and QDN-14B. This irrigation-like feature is inferred to result from enhanced methane flux in QDN-14A and QDN-14B. We infer that lateral migration of methane-rich fluids from R1 site to QDN-14A and QDN-14B sites together with upward migrated methane is responsible for the enhanced methane flux. This speculation is supported by the occurrence of gas hydrates which might have clogged the fluid channel in the seepage center (R1) and driven the transportation of methane-bearing fluid along a coarser sediment layer in surrounding sediments (QDN-14A and QDN-14B). The proposed scenario is further demonstrated using a non-steady-state modeling that reconstructed the porewater irrigation-like feature assuming an increased methane flux. The modeling result predicts that gas-hydrate formation in core R1 started at least 150 yr B.P. The proposed fluid flow pattern within a localized seep site may have a great implication for understanding the heterogeneity of sedimentary records.

Beschreibung: Highlights • δ13C, δ15N, and TOC/TN of POM suggest that the POM is characterized by a mixture of marine and terrestrial origins. • Hindcast model results revealed a major decrease in POC rain rate during the deglaciation–early Holocene transition. • The decrease in POC rain rate was induced by the decline in the terrestrial OM input associated with rapid sea level rise. Abstract Transient features in the organic carbon content of deep-sea sediment cores resulting from changes in the flux and/or quality of organic matter input are not uncommon. We examined the geochemical characteristics of sediments retrieved with a gravity core from the northwestern Solomon Sea (3908 m water depth), southern West Pacific Warm Pool (WPWP). δ13C and δ15N of sedimentary organic matter, together with TOC/TN data suggest that the organic material is characterized by a mixture of marine and terrestrial origins with a higher contribution from marine algae. The data were analyzed with an inverse non-steady-state reaction-transport model to examine the magnitude and variability of particulate organic carbon (POC) flux to the seafloor during the transition between the deglaciation period and early Holocene. Measured POC content and porewater NO3−, NH4+, DIC and SO42− concentrations were used to constrain the model. Hindcast results revealed that POC flux decreased from 75 to 37.5 μg cm−2 yr−1 during the deglaciation–early Holocene transition. The rate of POC degradation in the present setting is slightly lower compared to that in the pre-Holocene setting. The synchronous decline in the relative contribution of terrestrial organic matter input and rapid sea level rise during this transition suggest that sea level, rather than surface productivity, is the dominant factor controlling the POC deposition flux in the Solomon Sea. This is conceivable because the sampling site is proximal to high-relief islands with high rainfall, a well-developed submarine canyon system and narrow and steep continental margins. Consequently, we suggest that deep-water basins in proximity to similar high-relief mountainous islands in the tropical Pacific may represent important sinks for terrestrial organic material, especially during sea level lowstands.

Beschreibung: Methane of various origins is widespread in the sediments of continental margins, representing a key component of the carbon cycle in the ocean. Its occurrence in shallow marine sediments can be linked to the gas hydrate reservoir in the deep sedimentary column. However, this type of methane is difficult to track due to complex reactions occurred during its long distance migration. Porewater geochemical analyses of two ∼7 m piston cores (D17-15 and W01-16) combined with a reaction-transport model were applied to quantify methane-related biogeochemical processes and to explore the linkage of shallow methane to gas hydrate reservoir in the hydrate drilling areas of Shenhu and Dongsha in the South China Sea (SCS). The model results revealed that anaerobic oxidation of methane (AOM) is the predominant biogeochemical process in both cores, consuming approximately 85% and 74% of sulfate in the modeled domain, respectively. The crossplot of dissolve inorganic carbon (DIC) accumulation versus sulfate depletion of the system suggests that methane consumed during the AOM is mainly originated from external methane sources rather than local methanogenesis. Using a δ13CDIC mass balance calculation together with model-derived fractions of different DIC sources, we estimated that the δ13C value of the external methane in core D17-15 is −66.6‰, which is in accordance with the previous reported δ13C values of hydrate-bound methane in the area. These results suggest that methane consumed in shallow sediments in the hydrate drilling areas of the SCS is mainly originated from local gas hydrate reservoir. The proposed approach has the potential to be used to differentiate the sources of methane, which will provide constraints on dynamics of methane in gas hydrate-bearing marine sediments.