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: Published

Description: 36-47

Description: 3A. Geofisica marina e osservazioni multiparametriche a fondo mare

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

Description: The knowledge of the phase behavior of carbon dioxide (CO2)-rich mixtures is a key factor to understand the chemistry and migration of natural volcanic CO2 seeps in the marine environment, as well as to develop engineering processes for CO2 sequestration coupled to methane (CH4) production from gas hydrate deposits. In both cases, it is important to gain insights into the interactions of the CO2-rich phase—liquid or gas—with the aqueous medium (H2O) in the pore space below the seafloor or in the ocean. Thus, the CH4-CO2 binary and CH4-CO2-H2O ternary mixtures were investigated at relevant pressure and temperature conditions. The solubility of CH4 in liquid CO2 (vapor-liquid equilibrium) was determined in laboratory experiments and then modelled with the Soave–Redlich–Kwong equation of state (EoS) consisting of an optimized binary interaction parameter kij(CH4-CO2) = 1.32 × 10−3 × T − 0.251 describing the non-ideality of the mixture. The hydrate-liquid-liquid equilibrium (HLLE) was measured in addition to the composition of the CO2-rich fluid phase in the presence of H2O. In contrast to the behavior in the presence of vapor, gas hydrates become more stable when increasing the CH4 content, and the relative proportion of CH4 to CO2 decreases in the CO2-rich phase after gas hydrate formation.

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: 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: The submersible Nautile completed 22 dives during the Nautilau cruise (R/V Nadir, April 17-May 10, 1989) for a detailed investigation of the southern Lau basin near Tonga. The objective of the scientific team from France, Germany, and Tonga was to understand the process of sea-floor ore formation associated with hydrothermal circulation along the Valu Fa back-arc ridge behind the Tonga- Kermadec trench. The four diving areas, between lat 21°25′S and 22°40′S in water ∼2000 m deep, were selected on the basis of results from cruises of the R/V JeanCharcot and R/V Sonne. The Nadir cruise provided proof of hydrothermal activity—in all four areas, over more than 100 km—as indicated by the widespread occurrence of hydrothermal deposits and by heat flow, conductivity, and temperature measurements near the sea bottom. The most spectacular findings were high-temperature white and black smokers and associated fauna and ore deposits. Hydrothermal water chemistry and sulfide composition data presented here indicate that this hydrothermal field is very different from the hydrothermal fields in oceanic ridges. This difference is seen in the water chemistry of the hydrothermal fluid (pH = 2 and high metal content) and the chemical composition of sulfides (enrichment in Ba, As, and Pb).

Description: Within the Sea of Marmara, the highly active North Anatolian Fault (NAF) is responsible for major earthquakes (Mw ≥ 7), and acts as a pathway for fluid migration from deep sources to the seafloor. This work reports on pore water geochemistry from three sediment cores collected in the Gulfs of Izmit and Gemlik, along the Northern and the Middle strands of the NAF, respectively. The resulting data set shows that anaerobic oxidation of methane (AOM) is the major process responsible for sulfate depletion in the shallow sediment. In the Gulf of Gemlik, depth concentration profiles of both sulfate and alkalinity exhibit a kink-type profile. The Sulfate Methane Transition Zone (SMTZ) is located at moderate depth in the area. In the Gulf of Izmit, the low concentrations observed near the seawater-sediment interface for sulfate, calcium, strontium, and magnesium result from rapid geochemical processes, AOM, and carbonate precipitation, occurring in the uppermost part of the sedimentary column and sustained by free methane accumulation. Barite dissolution and carbonate recrystallization have also been identified at deeper depth at the easternmost basin of the Gulf of Izmit. This is supported by the profile of the strontium isotope ratios (87Sr/86Sr) as a function of depth which exhibits negative anomalies compared to the modern seawater value. The strontium isotopic signature also shows that these carbonates had precipitated during the reconnection of the Sea of Marmara with the Mediterranean Sea. Finally, a first attempt to interpret the sulfate profiles observed in the light of the seismic activity at both sites is presented. We propose the hypothesis that seismic activity in the areas is responsible for the transient sulfate profile, and that the very shallow SMTZ depths observed in the Gulf of Izmit is likely due to episodic release of significant amount of methane.

Description: Understanding the dynamics and fate of methane (CH 4 ) release from oceanic seepages on margins and shelves into the water column, and quantifying the budget of its total discharge at different spatial and temporal scales, currently represents a major scientific undertaking. Previous works on the fate of methane escaping from the seafloor underlined the challenge in both, estimating its concentration distribution and identifying gradients. In April 2019, the Envri Methane Cruise has been conducted onboard the R/V Mare Nigrum in the Western Black Sea to investigate two shallow methane seep sites at ∼120 m and ∼55 m water depth. Dissolved CH 4 measurements were conducted with two continuous in-situ sensors: a membrane inlet laser spectrometer (MILS) and a commercial methane sensor (METS) from Franatech GmbH. Additionally, discrete water samples were collected from CTD-Rosette deployment and standard laboratory methane analysis was performed by gas chromatography coupled with either purge-and-trap or headspace techniques. The resulting vertical profiles (from both in situ and discrete water sample measurements) of dissolved methane concentration follow an expected exponential dissolution function at both sites. At the deeper site, high dissolved methane concentrations are detected up to ∼45 m from the seabed, while at the sea surface dissolved methane was in equilibrium with the atmospheric concentration. At the shallower site, sea surface CH 4 concentrations were four times higher than the expected equilibrium value. Our results seem to support that methane may be transferred from the sea to the atmosphere, depending on local water depths. In accordance with previous studies, the shallower the water, the more likely is a sea-to-atmosphere transport of methane. High spatial resolution surface data also support this hypothesis. Well localized methane enriched waters were found near the surface at both sites, but their locations appear to be decoupled with the ones of the seafloor seepages. This highlights the need of better understanding the processes responsible for the transport and transformation of the dissolved methane in the water column, especially in stratified water masses like in the Black Sea.

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.