ALBERT

Description: Highlights • Combining porewater geochemistry, geochemical modeling and subsurface geophysical data in order to understand the fluid flow system of Kerch seep area. • This seep area is not in steady state. • Methane transport is in the form of gas bubbles not porewater advection. • High surface temperatures are the result of hydrate formation and not an indication for elevated geothermal gradients. • Modeling says this seep is young (〈500 years old). Abstract High-resolution 3D seismic data in combination with deep-towed sidescan sonar data and porewater analysis give insights into the seafloor expression and the plumbing system of the actively gas emitting Kerch seep area, which is located in the northeastern Black Sea in around 900 m water depth, i.e. well within the gas hydrate stability zone (GHSZ). Our analysis shows that the Kerch seep consists of three closely spaced but individual seeps above a paleo-channel-levee system of the Don Kuban deep-sea fan. We show that mounded seep morphology results from sediment up-doming due to gas overpressure. Each of the seeps hosts its own gas pocket underneath the domes which are fed with methane of predominantly microbial origin along narrow pipes through the GHSZ. Methane transport occurs dominantly in the form of gas bubbles decoupled from fluid advection. Elevated sediment temperatures of up to 0.3 °C above background values are most likely the result of gas hydrate formation within the uppermost 10 m of the sediment column. Compared to other seeps occurring within the GHSZ in the Black Sea overall only scarce gas indications are present in geoacoustic and geophysical data. Transport-reaction modeling suggests that the Kerch seep is a young seep far from steady state and probably not more than 500 years old.

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.

Description: Highlights • In-situ temperature measurements were conducted at the Danube deep sea fan. • Operations were performed with the MARUM-MeBo200 seafloor drill rig. • The BSR is located ∼20 m below the current gas hydrate stability zone. • Seismic data suggest presence of shallower BSR-like events. Abstract Coring, geophysical logging, and in-situ temperature measurements were performed with the MARUM-MeBo200 seafloor rig to characterize gas hydrate occurrences in sediments of the Danube deep sea fan, off Romania, Black Sea. The new drilling data showed no evidence for significant gas hydrate saturations within the sediments but the presence of free gas at the depth of the bottom-simulating reflector (BSR). In-situ temperature and core-derived geochemical data suggest that the current base of the gas hydrate stability zone (BGHSZ) is ∼20 m shallower than the BSR. Investigation of the seismic data around the drill sites shows several locations where free gas previously trapped at a former BGHSZ migrated upwards forming a new reflection above the BSR. This shows that the gas hydrate system in the Danube deep sea fan is still responding to climate changes initiated at the end of the last glacial maximum.

Description: Hydroacoustic surveys at the accretionary wedge southwest of Taiwan reveal a confined active hydrocarbon seepage area of ~ 49,000 m 2 in ~ 1350 m water depth on the northern crest of the Four-Way Closure Ridge, which we call Yam Seep. In this study, multibeam and side-scan sonar data acquired during surveys with an autonomous underwater vehicle during an expedition with R/V Ocean Researcher I in 2017 showed that the area is characterized by rough topography and high seafloor backscatter. Seafloor observations with a video sled and sediment sampling with gravity corers and the MeBo seafloor drill rig during an expedition with R/V SONNE in 2018 revealed that the area is almost entirely covered by intensely fractured methane-derived carbonates, which indicate that seepage has been ongoing for thousands of years. Hydroacoustic anomalies (‘flares’) in the water column indicated the presence of several gas bubble emission sites mostly at the center and eastern flank of the area in 2019. Drilling through massive carbonates in the northwestern part of Yam Seep induced free gas escape from a depth of ~ 5.1 m. This suggests the presence of gas hydrates in the subsurface as the seep area is located well within the gas hydrate stability zone. The inter-disciplinary investigations of the Yam Seep demonstrate that upward migration of light hydrocarbons and seafloor discharge has a considerable influence on the seabed properties.

Description: Seafloor heat flow measurements are utilized to determine the geothermal regime of the Danube deep-sea fan in the western Black Sea and are presented in the larger context of regional gas hydrate occurrences. Heat flow data were collected across paleo-channels in water depths of 550–1460 m. Heat flow across levees ranges from 25 to 30 mW m−2 but is up to 65 mW m−2 on channel floors. Gravity coring reveals sediment layers typical of the western Black Sea, consisting of three late Pleistocene to Holocene units, notably red clay within the lowermost unit cored. Heat flow derived from the bottom-simulating reflector (BSR), assumed to represent the base of the gas hydrate stability zone (GHSZ), deviates from seafloor measurements. These discrepancies are linked either to fast sedimentation or slumping and associated variations in sediment physical properties. Topographic effects account of up to 50% of heat flow deviations from average values. Combined with climate-induced variations in seafloor temperature and sea-level since the last glacial maximum large uncertainties in the prediction of the base of the GHSZ remain. A regional representative heat flow value is ~30 mW m−2 for the study region but deviations from this value may be up to 100%.

Description: Highlights • Four seafloor hydrocarbon emissions in the Eastern Black Sea were investigated • Eocene and/or Oligocene-Miocene Formations are most likely sources for oil and gas • Mixed secondary microbial and oil-associated thermogenic hydrocarbons at all sites • Site-specific light hydrocarbon compositions result from different mixing ratios Abstract Numerous hydrocarbon seep sites at the continental shelf, slope, and in the deep water basin are known to feed the Black Sea water reservoir of dissolved methane. In this study, we identified the likely sources of gas and oil that are emitted at four sites located on the continental slope offshore Georgia in the Eastern Black Sea at 830 to 1,140 m water depth – an area with gas seepage only (Batumi seep area) and three areas of joint gas and oil seepage (Iberia Mound, Colkheti Seep, and Pechori Mound). The geochemistry of bulk parameters, organic fractions and individual hydrocarbon biomarkers in near-surface sediments and of gas/oil expelled from the seafloor was analyzed and jointly interpreted to assign most likely hydrocarbon source rocks in the studied region. Presence of oleanane in shallow oil-impregnated sediments and oil slicks attests that the source rock at all sites is younger than Mid Cretaceous in age. We conclude that hydrocarbons ascending at all the four seepage areas originate from the Eocene Kuma Formation and/or the Oligocene–Lower Miocene Maikop Group, which are considered the principal hydrocarbon sources in the Eastern Black Sea region. Distributions of crude oil biomarkers in shallow sediments suggests moderate to heavy biodegradation. C1/C2+ ratios (10 to 4,163) along with stable C and H isotopic ratios (δ13C-CH4 ‒46.3 to ‒53.1.3‰ V-PDB; δ2H-CH4 ‒159 to ‒178‰ SMOW) indicate gas mixtures of oil-associated thermogenic and secondary microbial light hydrocarbons that are discharged from the four seep sites. Light hydrocarbons discharged at the Batumi Seep area are characterized by significant enrichments of methane, but almost similar δ13C-CH4 values if compared to the other study sites. Such methane enrichments likely result from a comparably higher degree of petroleum degradation and associated formation of secondary microbial methane.

Description: Highlights • Extensive asphalt deposits and asphalt volcanism at Mictlan Knoll in the southern Gulf of Mexico. • A novel type of active hydrocarbon seepage system in the southern GoM. • High-resolution seafloor mapping and seafloor manifestation of heterogeneous hydrocarbon seepage system. • Mapping, quantification and monitoring of gas emission sites in the southern GoM. • Mictlan Knoll hosts the most extensive asphalt deposits known to date in the GoM. Abstract Hydrocarbon seepage plays an essential role in defining seafloor morphology and increasing habitat heterogeneity in the deep sea whereby asphalt volcanism ranks among the most complex and proliferous hydrocarbon discharge systems that have been described to date. In this study, seepage of hydrocarbon gas and oil as well as asphalt deposits were investigated at Mictlan Knoll in the southern Gulf of Mexico. A multi-disciplinary approach was used including hydroacoustic surveys and visual seafloor observations to study the seafloor manifestations of hydrocarbon seepage. Mictlan Knoll is an asphalt volcano characterized by a crater-like depression surrounded by an elevated rim. Asphalt deposits are widespread in the depression where a large area of extensive asphalt deposits correlates with a high backscatter area (~75,000 m2). Numerous asphalt deposits appear relatively fresh and probably extruded recently, as oil bubbles were seen to emanate locally within areas covered by extensive asphalt deposits. An area of more irregular seafloor morphology occurring in the northern part of the depression is interpreted to be related to the active extrusion of asphalt below or within older surficial deposits. Additionally, 25 hydroacoustic anomalies indicative for gas bubble emissions were detected. Gas volume quantifications conducted during seafloor inspections with a remotely-operated vehicle (ROV) at a single gas escape site situated above a gas hydrate outcrop revealed up to 0.1 × 106 mol CH4/yr. Gas emission at this site, monitored by an autonomous scanning sonar device, indicated a highly variable bubble release activity. Based on our findings, it is proposed that Mictlan Knoll hosts the most extensive asphalt deposits known to date in the Gulf of Mexico.

Description: Hydrothermal fluid samples were retrieved during dives made by the remotely operated vehicle (ROV) QUEST (MARUM, University of Bremen) during the HYDROMAR I (M60/3, 2004) and HYDROMAR II (M64/2, 2005) cruises to the Logatchev hyrothermal field. The samples were retrieved using a pumped flow-through system (Kiel Pumping System KIPS) specially designed for the ROV QUEST. Once on board the ship, the liquids intended for microbiological studies were concentrated on 0.2 µm pore size polycarbonate filters (Sartorius) and stored at -20°C. The pH and sulfide concentrations were determined immediately after sample recovery. The pH was measured (Mettler electrodes with Ag/AgCl reference electrode) at 25°C in unfiltered sample aliquots. Sulfide concentrations were determined photometrically following the methylene blue method or, for samples with low concentrations, by voltammetry (Metrohm Application Bulletin 199/3e). Methane was analyzed on board by applying a purge and trap technique. For on-board measurements of dissolved hydrogen the water sample was degassed into a high-grade vacuum. Aliquots of the released gas were analyzed by gas chromatography (Thermo Electron Corporation Trace GC Ultra with a pulsed discharge detector). The abundance of bacterial and archaeal taxa was investigated by sequencing of the 16S rRNA gene. The diversity of the cbbL, cbbM and aclb was investigated by sequencing of the genes.