The Potential for Abiotic Methane in Arctic Gas Hydrates

Most methane enclosed in gas hydrates is biotic in origin, formed by microbial degradation of sedimentary organic matter. Increasingly, there is evidence that substantial gas hydrate may also be sourced from thermogenic decomposition of organic matter and subsequent migration of this gas into the gas hydrate stability zone. In addition, there is a third potential source of methane that does not involve organic matter at all— abiotic methane, which can be generated by magmatic processes or gaswater- rock reactions in the crust and upper mantle

Role of tectonic stress in seepage evolution along the gas hydrate‐charged Vestnesa Ridge, Fram Strait

Methane expulsion from the world ocean floor is a broadly observed phenomenon known to be episodic. Yet the processes that modulate seepage remain elusive. In the Arctic offshore west Svalbard, for instance, seepage at 200–400 m water depth may be explained by ocean temperature‐controlled gas hydrate instabilities at the shelf break, but additional processes are required to explain seepage in permanently cold waters at depths \u3e1000 m. We discuss the influence of tectonic stress on seepage evolution along the ~100 km long hydrate‐bearing Vestnesa Ridge in Fram Strait. High‐resolution P‐Cable 3‐D seismic data revealed fine‐scale (\u3e10 m width) near‐vertical faults and fractures controlling seepage distribution. Gas chimneys record multiple seepage events coinciding with glacial intensification and active faulting. The faults document the influence of nearby tectonic stress fields in seepage evolution along this deepwater gas hydrate system for at least the last ~2.7 Ma

3‐D Seismic Investigation of a Gas Hydrate and Fluid Flow System on an Active Mid‐Ocean Ridge; Svyatogor Ridge, Fram Strait

Tectonic settings play a large role in the development of fluid flow pathways for gas migrating through sedimentary strata. Gas hydrate systems worldwide are located on either the slopes of passive continental margins, often in large contourite deposits, or in accretionary wedges on subduction margins. The Svyatogor Ridge, however, located at the northwestern flank of the Knipovich Ridge and south of the Molloy Transform Fault (Fram Strait), is a gas hydrate system which is located on an actively spreading margin. Svyatogor Ridge has evidence of shallow gas accumulations; a strong BSR indicating a gas hydrate and underlying free gas system, and fluid flow pathways to the seafloor culminating in pockmarks. Using a high‐resolution P‐Cable 3‐D seismic survey, we investigate how tectonic and sedimentary regimes have influenced the formation of this well‐developed gas hydrate system. Large‐scale basement faults identified in the seismic data are interpreted as detachment faults, which have exhumed relatively young ultramafic rocks. These detachment faults act as conduits for fluid flow, and are responsible for the formation of folds in the overlying sediments that are breached by faults. We propose a model for fluid flow within this system whereby as sedimentary faults breach upward through the sedimentary strata, fluid is able to migrate further upward. We find that the tectonic regime on Svyatogor Ridge is the dominant driver of fluid migration and episodic release at the seafloor

Phosphatidylserine-exposing extracellular vesicles in body fluids are an innate defence against apoptotic mimicry viral pathogens

Some viruses are rarely transmitted orally or sexually despite their presence in saliva, breast milk, or semen. We previously identified that extracellular vesicles (EVs) in semen and saliva inhibit Zika virus infection. However, the antiviral spectrum and underlying mechanism remained unclear. Here we applied lipidomics and flow cytometry to show that these EVs expose phosphatidylserine (PS). By blocking PS receptors, targeted by Zika virus in the process of apoptotic mimicry, they interfere with viral attachment and entry. Consequently, physiological concentrations of EVs applied in vitro efficiently inhibited infection by apoptotic mimicry dengue, West Nile, Chikungunya, Ebola and vesicular stomatitis viruses, but not severe acute respiratory syndrome coronavirus 2, human immunodeficiency virus 1, hepatitis C virus and herpesviruses that use other entry receptors. Our results identify the role of PS-rich EVs in body fluids in innate defence against infection via viral apoptotic mimicries, explaining why these viruses are primarily transmitted via PS-EV-deficient blood or blood-ingesting arthropods rather than direct human-to-human contact

Donor-Flexible Nitrogen Ligands for Efficient Iridium-Catalyzed Water Oxidation Catalysis

A pyridylideneamide ligand with variable donor properties owing to a pronounced zwitterionic and a neutral diene-type resonance structure was used as a dynamic ligand at a Cp* iridium center to facilitate water oxidation catalysis, a reaction that requires the stabilization of a variety of different iridium oxidation states and that is key for developing an efficient solar fuel device. The ligand imparts high activity (nearly three-fold increase of turnover frequency compared to benchmark systems), and exceptionally high turnover numbers, which indicate a robust catalytic cycle and little catalyst degradation

Iridium Complexes Containing Mesoionic C Donors: Selective C(sp3)-H versus C(sp2)-H Bond Activation, Reactivity Towards Acids and Bases, and Catalytic Oxidation of Silanes and Water

Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp3)[BOND]H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp2)[BOND]H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp2)[BOND]H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D+ and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir[BOND]C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6 000 h−1 with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue.European Research CouncilScience Foundation IrelandNational Science Foundatio

Svyatogor Ridge—A Gas Hydrate System Driven by Crustal Scale Processes

Svyatogor Ridge is a gas hydrate-bearing sediment drift on the flank of an ultra-slow spreading mid-ocean ridge. Svyatogor Ridge hosts shallow gas accumulations, a strong bottom simulating reflection and fluid flow pathways (predominantly chimneys and faults) to the seafloor, culminating in pockmarks. Large offset detachment faults underlying Svyatogor Ridge provide access to deeper crustal and mantle ultramafic rocks, likely acting as conduits for warm fluid (and possible abiotic methane produced via serpentinization) to reach the shallow subsurface. This environment is distinct compared to other Arctic gas hydrate systems as it rests on the flank of an active mid-oceanic spreading ridge. It is the only known gas hydrate-bearing sediment drift in the Arctic where crustal-scale processes (mid-ocean ridge spreading) directly control the pressure and temperature regime for gas hydrate formation as well as fluid flow dynamics at the site