Description: MarsiteCruise was undertaken in October/November 2014 in the Sea of Marmara to gain detailed insight into the fate of fluids migrating within the sedimentary column and partially released into the water column. The overall objective of the project was to achieve a more global understanding of cold-seep dynamics in the context of a major active strike-slip fault. Five remotely operated vehicle (ROV) dives were performed at selected areas along the North Anatolian Fault and inherited faults. To efficiently detect, select and sample the gas seeps, we applied an original procedure. It combines sequentially (1) the acquisition of ship-borne multibeam acoustic data from the water column prior to each dive to detect gas emission sites and to design the tracks of the ROV dives, (2) in situ and real-time Raman spectroscopy analysis of the gas stream, and (3) onboard determination of molecular and isotopic compositions of the collected gas bubbles. The in situ Raman spectroscopy was used as a decision-making tool to evaluate the need for continuing with the sampling of gases from the discovered seep, or to move to another one. Push cores were gathered to study buried carbonates and pore waters at the surficial sediment, while CTD-Rosette allowed collecting samples to measure dissolved-methane concentration within the water column followed by a comparison with measurements from samples collected with the submersible Nautile during the Marnaut cruise in 2007. Overall, the visited sites were characterized by a wide diversity of seeps. CO2- and oil-rich seeps were found at the westernmost part of the sea in the Tekirdag Basin, while amphipods, anemones and coral populated the sites visited at the easternmost part in the Cinarcik Basin. Methane-derived authigenic carbonates and bacterial mats were widespread on the seafloor at all sites with variable size and distributions. The measured methane concentrations in the water column were up to 377 μmol, and the dissolved pore-water profiles indicated the occurrence of sulfate depleting processes accompanied with carbonate precipitation. The pore-water profiles display evidence of biogeochemical transformations leading to the fast depletion of seawater sulfate within the first 25-cm depth of the sediment. These results show that the North Anatolian Fault and inherited faults are important migration paths for fluids for which a significant part is discharged into the water column, contributing to the increase of methane concentration at the bottom seawater and favoring the development of specific ecosystems.

Description: Extensive seafloor authigenic carbonate crusts occur as pavements, mounds and chimneys along the North Anatolian Fault System (NAFS) in the Sea of Marmara. They are often covered or surrounded by patches of black Fe-sulphide-rich sediments, and associated with hydrocarbon-rich gas and brackish-water emissions in the 1250 m-deep deep basins and with deep saline formation waters and hydrocarbons emissions from mud volcanoes and anticlines on the 350–650 m-deep compressional highs. The authigenic carbonate crusts are commonly porous with sinter-like, botryoidal and sugary- granular textures, and constructed from cementation of framework elements consisting mainly of bivalve shells and shell fragments, serpulid tubes, fibrous microbial organic matter and rarely pebbles. The authigenic cements consist mainly of aragonite in most sites, but high Mg-calcite occurs as a major carbonate cement at some basinal sites, where the brackish former Marmara “Lake” waters emerge. The buoyant emission of brackish waters in the deep Marmara basins and deeply sourced fluids from the Tertiary Thrace basin at the compressional highs are supported by relatively low δ18O values (+0.5‰ to +3.8‰ V-PDB, average = +2.1‰V-PDB, n = 24) of carbonates in the former and high values (+2.6‰ to +3.4‰ V-PDB, average = +3.0‰, n = 9) in the latter areas. Low δ13C values (−47.6‰ to −13.7‰ V-PDB, average: −34.9‰ V-PDB, n = 33) and close association with black reduced sediments indicate that the seafloor authigenic carbonates are formed by the anaerobic oxidation of methane (AOM) at or near the seafloor, as result of high methane flux, possibly during periods of high seismic activity. Authigenic carbonates from the Western and Central highs are relatively less depleted in 13C than those of the deep basin sites, suggesting both microbial and thermogenic methane source for the deep basins carbonates and mainly thermogenic hydrocarbon, with some contribution from the biodegradation of heavy hydrocarbons and gas hydrate dissociation, for carbonates from the compressional highs. U-Th ages of the authigenic carbonates range from less than 1 ka BP to 9.6 ka BP. The age distribution, together with the geochemical and mineralogical data, suggests that different processes such as seismo-tectonics and gas hydrates destabilization might have played important role in the authigenic carbonate formation in the Sea of Marmara over the last 10 ka.

Description: On continental margins, upward migration of fluids from various sources and various subsurface accumulations, through the sedimentary column to the seafloor, leads to the development of cold seeps where chemical compounds are discharged into the water column. MarsiteCruise was undertaken in November 2014 to investigate the dynamics of cold seeps characterized by vigorous gas emissions in the Sea of Marmara (SoM).A previous paper published by Bourry et al. (2009) presented the gas geochemistry of three seeps sampled along three different segments in the SoM. Their findings showed that the seeps were sourced by three different reservoirs. In this paper, seventeen seeps were investigated to determine the gas sources, unravel reservoir contributions, and estimate their level of mixing. The molecular and stable isotope compositions of the gas compounds were determined to establish the empirical diagrams that usually allow to delineate source domains. The results provide insights into the complexities of source mixing within the sedimentary column of the SoM before emission of the gases into the water column. The seep gases originate from deep thermogenic or microbial hydrocarbon sources, or from a CO2-rich source. Microbial sources producing methane from primary methanogenesis have been identified in the Tekirdağand the Çinarcik basins. In addition, six different thermogenic reservoirs or six different pathways of migration are responsible for the supply of gas to the seeps on the highs and in the western basin. Five of them are undergoing biodegradation followed by secondary methanogenesis, thereby providing additional sources of microbial methane to the seeps. Overall, the gases emitted by the seventeen seeps consist of variable mixtures of different components from two or three sources.

Description: Highlights • Geochemical analyses highlight multiple diagenesis processes occurring in the sediment. • Intense methane seepages and organic matter degradation contribute to the sulfate reduction. • Chemical of dissolved and mineral iron species indicate that iron is associated with clay minerals. • In response to seawater intrusion, ion exchange, dissolution and reverse weathering reactions change the composition of clay constituting the sediment. Abstract Pore water and sediment geochemistry in the western Black Sea were investigated on long Calypso piston core samples. Using this type of coring device facilitates the recovery of the thick sediment record necessary to analyze transport-reaction processes in response to the postglacial sea-level rise and intrusion of Mediterranean salt water 9 ka ago, and thus, to better characterize key biogeochemical processes and process changes in response to the shift from lacustrine to marine bottom water composition. Complementary data indicate that organic matter degradation occurs in the upper 15 m of the sediment column. However, sulfate reduction coupled with Anaerobic Methane Oxidation (AOM) is the dominant electron-accepting process and characterized by a shallow Sulfate Methane Transition Zone (SMTZ). Net silica dissolution, total alkalinity (TA) maxima and carbonate peaks are found at shallow depths. Pore water profiles clearly show the uptake of K+, Mg2+ and Na + by, and release of Ca2+ and Sr2+ from the heterogeneous lacustrine sediments, which is likely controlled by chemical reactions of silicate minerals and changes in clay mineral composition. Iron (Fe2+) and manganese (Mn2+) maxima largely coincide with Ca2+ peaks and suggest a close link between Fe2+, Mn2+ and Ca2+ release. We hypothesize that the Fe2+ maxima below the SMTZ result from deep Fe3+ reduction linked to organic matter degradation, either driven by DOC escaping from the shallow sulfate reduction zone or slow degradation of recalcitrant POC. The chemical analysis of dissolved and solid iron species indicates that iron is essentially associated with clay minerals, which suggests that microbial iron reduction is influenced by clay mineral composition and bioavailability of clay mineral-bound Fe(III). Overall, our study suggests that postglacial seawater intrusion plays a major role in shaping redox zonation and geochemical profiles in the lacustrine sediments of the Late Quaternary.