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Shallow seabed depressions attributed to focused fluid seepage, known as pockmarks, have been documented in all continental margins. In this study we demonstrate how pockmark formation can be the result of a combination of multiple factors – fluid type, overpressures, seafloor sediment type, stratigraphy, and bottom currents. We integrate multibeam echosounder and seismic reflection data, sediment cores and pore water samples, with numerical models of groundwater and gas hydrates, from the Canterbury Margin (off New Zealand). More than 6800 surface pockmarks, reaching densities of 100 per km2, and an undefined number of buried pockmarks, are identified in the middle to outer shelf and lower continental slope. Fluid conduits across the shelf and slope include shallow to deep chimneys/pipes. Methane with a biogenic and/or thermogenic origin is the main fluid forming flow and escape features, although saline and freshened groundwaters may also be seeping across the slope. The main drivers of fluid flow and seepage are overpressure across the slope generated by sediment loading and thin sediment overburden above the overpressured interval in the outer shelf. Other processes (e.g. methane generation and flow, a reduction in hydrostatic pressure due to sea-level lowering) may also account for fluid flow and seepage features, particularly across the shelf. Pockmark occurrence coincides with muddy sediments at the seafloor, whereas their planform is elongated by bottom currents.

International audience; The Mozambique and Madagascar margins present major rivers that are responsible for the discharge of large amounts of terrestrial organic matter (OM) which can influence carbon cycling in marine environments. Therefore, the Mozambique channel represents a unique case to study the fate of the organic carbon in deepwater domains. Using a new and extensive data set of sedimentary OM collected from sediment traps, seafloor sediments and core sediments, we address the origin of the OM that is transported and deposited in the Mozambique Channel, its degradation state and preservation conditions. A Rock-Eval 6 survey allowed us to characterize the origin and amount of OM from shallow to deep-water turbidite systems, between 500 and 4400 m water depth. Rock-Eval 6 performed on suspended sediments within particle traps at 47 m above the seabed show that the OM is transported into the deep-water domain with relatively high TOC (between 1.5 and 2.5%). However, the OM is largely oxidized close to the water-sediment interface (Oxygen Index >300 mg CO 2 /g TOC). Seafloor sediments sampled to a maximum depth of 40 cm show lower TOC values compared to those collected from particle traps suggesting that the degradation of the OM is mainly active at the water-sediment interface. Small concentrations of OM are preserved within the recent sediments of the distal area of the Zambezi turbidite system below 2500 m water depth (TOC < 0.5%). Rock-Eval results show that core sediments from the Majunga slope (NW margin of Madagascar) and the Zambezi slope (Mozambique margin) contain the highest concentration of terrestrial OM (TOC between 1 and 2%). However, the OM within core sediments from the deep-water domain is largely oxidized and degraded, probably due to the conjugate effect of low sediment accumulation rates (SARs) and high permeabilities of the coarse-grained sediments. Consequently, the deep-water domain of the Mozambique Channel does not seem to be an important sink of terrestrial OM. This process is reinforced by important bottom water currents which induce the remobilization and transport of seafloor sediments that lead to higher oxygen exposure time in the uppermost centimeters of sediments.

International audience; Marine sediments near continental margins contain sedimentary organic matter (SOM) which is subject to the metabolic activity of micro-organisms during early diagenesis resulting in production of biogenic methane. This process occurs at microscopic scale and anaerobic conditions. Here, we apply a new numerical approach to simulate biogenic methane production offshore Aquitaine (Bay of Biscay) where gas seeps have been recently observed as the result of microbial activity. This new approach accounts for: (1) degradation of a labile-SOM fraction to methane, (2) first order kinetics of the thermal degradation of a thermo-labile-SOM fraction into labile fraction at greater burial and (3) decrease of SOM reactivity with time. First, the organic matter is characterized through pyrolysis using Rock-Eval performed on cuttings collected from two wells located within the methane seepage area. The microbial system is fed from a type III continental-derived SOM which is immature (average Tmax < 425 °C). The basin model is built and calibrated on seismic and well data. It accounts for the consumption of methane required to precipitate methane-derived authigenic carbonates which are found widely distributed on the seafloor as the result of the anaerobic oxidation of methane during upward migration. A sensitivity analysis is performed on the main model input parameters to quantify their impact on the biogenic gas production and expulsion/migration processes. Results led to a reference scenario for microbial gas production in offshore Aquitaine. With this model the generated methane is predominantly dissolved in water and transported by advective processes. Migration is mainly vertical from the source rock layers to the seafloor and controlled by sediment porosity and strata geometry. Modelling can reproduce natural processes such as gas migration at emission points (gas seeps) which have been previously mapped in the offshore Aquitaine Basin. Our results suggest that the biogenic methane is sourced by a present-day active system with a mean flow rate of 27 Mg/y which is relatively lower than flux modelled during the early Pleistocene reaching up to 41 Mg/y. Calculated total methane lost to the seafloor along the Aquitaine Shelf is in accordance with methane flow rate estimated from in situ measurements and acoustic signatures of bubbling sites, and ranges between 0.87 Tcf/My and 1.48 Tcf/My. Here we propose a new workflow to assess and predict biogenic gas occurrences in offshore environment at the basin scale where gas is sourced by recent continental-derived organic matter. This new approach can help to better assess the total biogenic methane budget emitted naturally in the shelf area of oceans that may reach the atmosphere with a negative impact on climate and environment.

International audience; Evidences for active fluid seepages have been discovered along the Zambezi continental slope (offshore Southern Mozambique). These seepages are mostly associated with pockmarks which are aligned along a trend parallel to the slope and running closely upstream of the headwall scarp of a wide zone of slope destabilization. Fluid seepages are interpreted as a potential trigger for the slope destabilization. Acoustic anomalies within the water column have been interpreted as related to moderate bubble seepages mostly located outside and only punctually inside the destabilization zone. Exploration with the SCAMPI towed camera system in the widest pockmark (diameter 200 m wide) has shown fluid seepages associated to authigenic carbonate crusts and possibly bacterial mats. These fluid seepages are also associated to the presence of chemiosynthetic organisms (Vesicomyidae and Thyasiridae bivalves, Siboglinidae tubeworms). The sampled gas in the sediment corresponds mainly to CH4 of microbial origin, generated by hydrogenotrophic methanogenesis from a substrate of organic origin, i.e. a conventional process of genesis of microbial gas in the marine domain. No evidence for thermogenic gas was detected. Another type of pockmarks has been observed within the core of the slope destabilization zone. Most of these pockmarks are inactive in terms of fluid seepage at present time and are associated to carbonate buildups forming chimney geometries. They probably correspond to diagenetic chimneys of former fluid migration pathways that have been exhumed during the mass sliding and the surrounding depression are related to recurrent activity of strong lateral slope currents which have scoured the sediments around. The spatial organization of the slope destabilization features is considered as representative of the temporal evolution of the landslide giving information about the dynamics of slope instability processes. This proposed evolution started by scattered seepages of formation water with dissolved gas. Then free gas seepages appeared notably in the upper part of the slope. This was followed by progressive shallow deformation in the sediments downslope of the main gas seepages. Finally, the whole slope was destabilized forming imbricated landslides exhuming locally former diagenetic chimneys.

While pH-driven interconversion of tetraquinoxaline cavitands (QxCav) from vase to kite conformation has been extensively studied both in solution and at interfaces, cavitands behavior in solid matrices is still unexplored. Therefore, the synthesis of a new class of quinoxaline cavitand based copolymers is here reported; a soluble linear poly(butyl methacrylate) (PBMA) and an insoluble cross-linked polydimethylsiloxane (PDMS), ensuring a convenient incorporation of the switchable unit, were chosen as polymer matrices. Conformational studies, performed both in solution and at the solid state, confirmed the retention of vase → kite switching behavior when moving from monomeric units to polymeric structures.

Active materials are those capable of giving some physical reaction under external stimuli coming from the environment such as temperature, pH, light, mechanical stress, etc. Reactive polymeric materials can be obtained through the introduction of switchable molecules in their network, i.e. molecules having two distinct stable conformations: if properly linked to the hosting polymer chains, the switching from one state to the other can promote a mechanical reaction of the material, detectable at the macroscale, and thus enables us to tune the response according to a desired functionality. In the present paper, the main aspects of the mechanical behavior of polymeric materials with embedded switchable molecules—properly linked to the polymer's chains—are presented and discussed. Starting from the micro mechanisms occurring in such active material, a continuum model is developed, providing a straightforward implementation in computational approaches. Finally, some experimental outcomes related to a switchable molecules (known as quinoxaline cavitands) added to an elastomeric PDMS under chemical stimuli, are presented and quantitatively discussed through the use of the developed mechanical framework.

The complexation between 2-ureido-4[1H]-pyrimidinone (UPy) and 2,7-diamido-1,8-naphthyridine (NaPy) is used to promote the mild chemisorption of a UPy-functionalized terbium(III) double decker system on a silicon surface. The adopted strategy allows the single-molecule magnet behavior of the system to be maintained unaltered on the surface.

The synthesis and the chemisorption from solution of a terbium bis‐phthalocyaninato complex suitable for the functionalization of lanthanum strontium manganite (LSMO) are reported. Two phosphonate groups are introduced in the double decker structure in order to allow the grafting to the ferromagnetic substrate actively used as injection electrode in organic spin valve devices. The covalent bonding of functionalized terbium bis‐phthalocyaninato system on LSMO surface preserves its molecular properties at the nanoscale. X‐ray photoelectron spectroscopy confirms the integrity of the molecules on the LSMO surface and a small magnetic hysteresis reminiscent of the typical single molecule magnet behavior of this system is detected on surface by X‐ray magnetic circular dichroism experiments. The effect of the hybrid magnetic electrode on spin polarized injection is investigated in vertical organic spin valve devices and compared to the behavior of similar spin valves embedding a single diamagnetic layer of alkyl phosphonate molecules analogously chemisorbed on LSMO. Magnetoresistance experiments have evidenced significant alterations of the magneto‐transport by the terbium bis‐phthalocyaninato complex characterized by two distinct temperature regimes, below and above 50 K, respectively.

The complexation between 2-ureido-4[1H]-pyrimidinone (UPy) and 2,7-diamido-1,8-naphthyridine (NaPy) is used to promote the mild chemisorption of a UPy-functionalized terbium(III) double decker system on a silicon surface. The adopted strategy allows the single-molecule magnet behavior of the system to be maintained unaltered on the surface.