ALBERT

Description: Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Description: The shrinking-core model of the formation of gas hydrates from ice spheres with well-defined geometry gives experimental access to the gas permeation in bulk hydrates which is relevant to their use as energy storage materials, their exploitation from natural resources, as well as to their role in flow assurance. Here we report on a new approach to model CO2 clathration experiments in the temperature range from 230 to 272 K. We develop a comprehensive description of the gas permeation based on the diffusion along the network of polyhedral cages, some of them being empty. Following earlier molecular dynamics simulation results, the jump from a cage to one of its empty neighbors is assumed to proceed via a “hole-in-cage-wall” mechanism involving water vacancies in cage walls. The rate-limiting process in the investigated temperature range can be explained by the creation of water-vacancy-interstitial pairs. The gas diffusion leads to a time-dependent cage filling which decreases across the hydrate layer with the distance from the particle surface. The model allows a prediction of the time needed for a complete conversion of ice spheres into clathrate as well as the time needed for a full equilibration of the cage fillings. The findings essentially support our earlier results obtained in the framework of a purely phenomenological permeation model in terms of the overall transformation kinetics, yet it provides for the first time insight into the cage equilibration processes. The diffusion of CO2 molecules through bulk hydrate is found to be about three to four times faster in comparison with the CH4 case.

Description: Marine macroalgae, seaweeds, are exceptionally prolific producers of halogenated natural products. Biosynthesis of halogenated molecules in seaweeds is inextricably linked to reactive oxygen species (ROS) signaling as hydrogen peroxide serves as a substrate for haloperoxidase enzymes that participate in the construction these halogenated molecules. Here, using red macroalga Asparagopsis taxiformis, a prolific producer of the ozone depleting molecule bromoform, we provide the discovery and biochemical characterization of a ROS-producing NAD(P)H oxidase from seaweeds. This discovery was enabled by our sequencing of Asparagopsis genomes, in which we find the gene encoding the ROS-producing enzyme to be clustered with genes encoding bromoform-producing haloperoxidases. Biochemical reconstitution of haloperoxidase activities establishes that fatty acid biosynthesis can provide viable hydrocarbon substrates for bromoform production. The ROS production haloperoxidase enzymology that we describe here advances seaweed biology and biochemistry by providing the molecular basis for decades worth of physiological observations in ROS and halogenated natural product biosyntheses.