Livio Ruffine

Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

Pore water geochemistry at two seismogenic areas in the Sea of Marmara

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.

Geochemical Dynamics of the Natural-Gas Hydrate System in the Sea of Marmara, Offshore Turkey

Natural-gas hydrate systems are solid-state light-hydrocarbon accumulations which are encountered in the permafrost and the continental margins. They are stable under highpressure and low-temperature conditions and represent the major hydrocarbon volume on earth (Kvenvolden, 1988). Gas hydrates consist of a polycrystalline structure where a light hydrocarbon is trapped within a water lattice. The nature of the hydrocarbons is strongly related to their origin which is either microbial (also called biogenic) or thermogenic. Microbial gas-hydrate systems contain hydrocarbons produced by bacteria and archaea. There are primarily methane with a very small amount of ethane and eventually propane (Max, 2003). Others non-hydrocarbon compounds like hydrogen sulphur and carbon dioxide are also present. In the case of microbial gases, the hydrates are formed at or near the gas production area. Owing to the very high-methane content, these hydrates are commonly called methane-hydrate systems.

Focused hydrocarbon‐migration in shallow sediments of a pockmark cluster in the Niger Delta (Off Nigeria)

The Niger Delta is one of the largest hydrocarbon basin offshore Africa and it is well known for the presence of active pockmarks on the seabed. During the Guineco-MeBo cruise in 2011, long cores were taken from a pockmark cluster in order to investigate the state of its current activity. Gas hydrates, oil and pore-water were sampled for geochemical studies. The resulting dataset combined with seismic data reveal that shallow hydrocarbon migration in the upper sedimentary section was focused exclusively within the pockmarks. There is a clear tendency for gas migration within the hydrate-bearing pockmarks, and oil migration within the carbonate-rich one. This trend is interpreted as a consequence of hydrate dissolution followed by carbonate precipitation in the course of the evolution of these pockmarks. We also demonstrate that Anaerobic Oxidation of Methane (AOM) is the main process responsible for the depletion of pore-water sulfate, with depths of the Sulfate-Methane Transition Zone (SMTZ) ranging between 1.8 and 33.4 m. In addition, a numerical transport-reaction model was used to estimate the age of hydrate-layer formation from the present-day sulfate profiles. The results show that the sampled hydrate-layers were formed between 21 and 3750 years before present. Overall, this work shows the importance of fluid flow on the dynamics of pockmarks, and the investigated cluster offers new opportunities for future cross-site comparison studies. Our results imply that sudden discharges of gas can create hydrate layers within the upper sedimentary column which can affect the seafloor morphology over few decades. This article is protected by copyright. All rights reserved.

New insights into the transport processes controlling the sulfate-methane-transition-zone near methane vents.

Over the past years, several studies have raised concerns about the possible interactions between methane hydrate decomposition and external change. To carry out such an investigation, it is essential to characterize the baseline dynamics of gas hydrate systems related to natural geological and sedimentary processes. This is usually treated through the analysis of sulfate-reduction coupled to anaerobic oxidation of methane (AOM). Here, we model sulfate reduction coupled with AOM as a two-dimensional (2D) problem including, advective and diffusive transport. This is applied to a case study from a deep-water site off Nigeria’s coast where lateral methane advection through turbidite layers was suspected. We show by analyzing the acquired data in combination with computational modeling that a two-dimensional approach is able to accurately describe the recent past dynamics of such a complex natural system. Our results show that the sulfate-methane-transition-zone (SMTZ) is not a vertical barrier for dissolved sulfate and methane. We also show that such a modeling is able to assess short timescale variations in the order of decades to centuries.

Gas Seepage along the Edge of the Aquitaine Shelf (France): Origin and Local Fluxes

During the scientific expedition GAZCOGNE2 at the Bay of Biscay nine gas seeps were sampled for the first time and their flux was measured using an in situ pressure-preservation sampler (PEGAZ, ©IFREMER). Overall, three sites were investigated to determine the nature and the origin of the gases bubbling at the seafloor and forming acoustic plumes into the water column, as this was the question raised from the first geologic study of the area. This has guided our study and accordingly corresponds to the main purpose of the present article. Thus, the molecular and isotopic (δD and δ13C) analyses revealed that the gas seeps were primarily composed of methane. Both methane and ethane are of microbial origin, and the former has been generated by microbial reduction of carbon dioxide. Heavier hydrocarbons accounted for less than 0.06% mol of the total amount. Despite the microbial origin of methane, the samples exhibit subtle differences with respect to the values, which varied between −72.7 and −66.1 . It has been suggested that such a discrepancy was predominantly governed by the occurrence of anaerobic methane oxidation. The PEGAZ sampler also enabled us to estimate the local gas fluxes from the sampled streams. The resulting values are extremely heterogeneous between seeps, ranging from 35 to 368 mLn·min−1. Assuming a steady discharge, the mean calculated methane emission for the nine seeps is of 38 kmol·yr−1. Considering the extent of the seep area, this very local estimate suggests that the Aquitaine Shelf is a very appropriate place to study methane discharge and its fate on continental shelves.

Freshwater lake to salt-water sea causing widespread hydrate dissociation in the Black Sea

Gas hydrates, a solid established by water and gas molecules, are widespread along the continental margins of the world. Their dynamics have mainly been regarded through the lens of temperature-pressure conditions. A fluctuation in one of these parameters may cause destabilization of gas hydrate-bearing sediments below the seafloor with implications in ocean acidification and eventually in global warming. Here we show throughout an example of the Black Sea, the world’s most isolated sea, evidence that extensive gas hydrate dissociation may occur in the future due to recent salinity changes of the sea water. Recent and forthcoming salt diffusion within the sediment will destabilize gas hydrates by reducing the extension and thickness of their thermodynamic stability zone in a region covering at least 2800 square kilometers which focus seepages at the observed sites. We suspect this process to occur in other world regions (e.g., Caspian Sea, Sea of Marmara).Gas hydrates are maintained via a balance of temperature and pressure, if this changes then destabilization may occur. Here, the authors show instead that due to recent changes in the salinity of the sea water of the Black Sea, gas hydrates may become destabilized with widespread methane seepage.

Gas and seismicity within the Istanbul seismic gap

Understanding micro-seismicity is a critical question for earthquake hazard assessment. Since the devastating earthquakes of Izmit and Duzce in 1999, the seismicity along the submerged section of North Anatolian Fault within the Sea of Marmara (comprising the “Istanbul seismic gap”) has been extensively studied in order to infer its mechanical behaviour (creeping vs locked). So far, the seismicity has been interpreted only in terms of being tectonic-driven, although the Main Marmara Fault (MMF) is known to strike across multiple hydrocarbon gas sources. Here, we show that a large number of the aftershocks that followed the M 5.1 earthquake of July, 25th 2011 in the western Sea of Marmara, occurred within a zone of gas overpressuring in the 1.5–5 km depth range, from where pressurized gas is expected to migrate along the MMF, up to the surface sediment layers. Hence, gas-related processes should also be considered for a complete interpretation of the micro-seismicity (~M < 3) within the Istanbul offshore domain.