Description: We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s→l) → CH4·6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25−30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140−200 K, Pc = 50−100 MPa, and ε = 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 an unusually high 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: In both terrestrial and aquatic environments introductions of non-indigenous species are continuing and represent one important component of global change. Negative biotic interactions by resident species may prevent successful invaders from becoming pests. Few experimental data are available on the presence and significance of such biotic resistance other than predation or competition. This study addresses the role of habitat structure provided by a native eelgrass (Zostera marina) canopy on growth and survival of the non-indigenous mussel Musculista senhousia, a habitat-modifying gregarious suspension feeder with strong effects on native infauna and eelgrass. In 2 southern California bays, a series of transplantation experiments using tagged mussels revealed that inside an eelgrass canopy, Musculista growth rates were reduced by more than half in 3 of 4 experiments compared to adjacent unvegetated areas. Musculista survival also decreased inside the vegetation in a 4-mo experiment. As one element of habitat structure, we tested the effects of eelgrass patch size, using natural (1 site) and planted (1 site) eelgrass patches of defined sizes. Growth rates of Musculista were highest outside the vegetation and decreased as eelgrass patch size increased. As a potential mechanism for the canopy effects, we suggest that Musculista receives less food inside the vegetation. In the experimental plots, the presence and spatial extent of the macrophyte canopy strongly affected near bottom (10 cm) horizontal water flow assessed with a direct dye tracking method. Reduced mussel growth rates were linearly associated with lower water flow, and presumably, food flux. Over a period of 7 mo, food resources (particulate chlorophyll a) were consistently lower 1 and 5 cm above the sea floor inside eelgrass patches compared to the sand flat. The reduction in food availability matched the growth reduction of Musculista. Also, mussel condition (dry flesh mass/shell mass) was worse in individuals growing in eelgrass than in the sand flat. Previous experiments revealed that dense beds of Musculista impede the rhizome growth and vegetative propagation of eelgrass, yet mussels attain abundances sufficient for interference only if eelgrass beds are patchy. Thus, anthropogenic disturbances on eelgrass beds, which often result in meadow fragmentation, and the proliferation of Musculista may have synergistic negative effects on the persistence of eelgrass beds.

Description: An automated method for on-site monitoring of uranium(VI) in raffinate streams originating from nuclear fuel reprocessing plants is described. An in-line stripping procedure (based on liquid/liquid extraction) was developed to extract U(VI) from this stream, a solvent mixture of 20% tributyl phosphate and nitric acid in kerosene, into an aqueous sodium sulfate solution, Degradation products in the solvent mixture, especially dibutyl phosphate, give rise to very strong complexes and are responsible for moderate but constant U(VI) recoveries (similar to 50%), Optimal conditions for in-line stripping comprise a mixing ratio of extractant (0.5 M sodium sulfate in water)/solvent mixture of similar to 3 and a pumping rate of similar to 0.4 mL min(-1) of the solvent mixture. The determination of U(VI) was by on-line cathodic stripping voltammmetry (CSV), preceded by adsorptive collection of the U(VL) as an oxine complex onto a hanging mercury drop electrode, Quantities of 1-2 mL of the aqueous extract were pumped into the voltammmetric cell and diluted (1/5 to 1/10) with a background electrolyte containing 0.1 M PIPES buffer, 2 x 10(-4) M oxine, 10(-4) M EDTA, and 0.2 M hydrazine hydrate (pH 9.0), The CSV peak for U(VI) was obtained at -0.68 V with a detection limit of 20 nM in the raffinate stream using an adsorption time of 120 s, Both the inline stripping procedure and the on-line measurement were fully automated, with a relative standard deviation in the measurements of 〈 5%.

Description: Six new labdane diterpenoids, leopersin C (1), 15-epi-leopersin C (2), leopersin D (3), leopersin E (4), leopersin F (5), and 7-epi-leopersin F (6) were isolated from the aerial parts of Leonurus persicus. Their structures were elucidated by extensive use of 1D and 2D homonuclear and heteronuclear shift-correlated 1H−13C-NMR spectroscopic methods. Leopersin C (1) and 15-epi-leopersin C (2) were obtained as a C-15 epimeric mixture, and their structures were elucidated on this basis.

Description: Seven new labdane diterpenoids, leopersin G−L (1−4, 6−7) and 15-epi-leopersin J (5), and two known ones, 13-hydroxyballonigrinolide (8) and ballotenol (9), were isolated from the aerial parts of Leonurus persicus along with β-sitosterol and stigmasterol. The structure determinations were mainly based on 1D and 2D NMR spectra. The stereochemical configuration of ballotenol (9) was reestablished by 2D ROESY spectroscopy and by single-crystal X-ray diffraction analysis.

Description: Two new iridoid glucosides, 6-O-acetylajugol (1) and 7,8-epoxy-8-epi-loganic acid (2), together with five known iridoid glucosides, galiridoside (3), ajugoside (4), 10-deoxygeniposidic acid (5), 7-deoxy-8-epi-loganic acid (6), and 8-O-acetylharpagide (7), have been isolated from the aerial parts of Leonurus persicus. Leucosceptoside A (8), eugenyl β-rutinoside (9), and kaempferol 3-O-glucoside (10) were also isolated. The structures of 1 and 2 were elucidated by extensive 1D- and 2D-NMR spectroscopy and molecular modeling. The structure of 3 was confirmed by single-crystal X-ray diffraction. Antimicrobial activity of compounds (1−10) was also evaluated against a panel of Gram-positive and Gram-negative bacteria and two strains of fungi.

Description: An overview is provided of time-independent physical/chemical properties as related to crystal structures. The following two points are illustrated in this review:  (1) Physical and chemical properties of structure I (sI) and structure II (sII) hydrates are well-defined; measurements have begun on sH. Properties of sI and sII are determined by the molecular structures, described by three heuristics:  (i) Mechanical properties approximate those of ice, perhaps because hydrates are 85 mol % water. Yet each volume of hydrate may contain as much as 180 volumes (STP) of the hydrate-forming species. (ii) Phase equilibrium is set by the size ratio of guest molecules within host cages, and three-phase (Lw−H−V) equilibrium pressure depends exponentially upon temperature. (iii) Heats of formation are set by the hydrogen-bonded crystals and are reasonably constant within a range of guest sizes. (2) Fundamental research challenges are (a) to routinely measure the hydrate phase (via diffraction, NMR, Raman, etc.), and (b) to formulate an acceptable model for hydrate formation kinetics. The reader may wish to investigate details of this review further, via references contained in several recent monographs.

Description: We propose that ocean conditions of the Near Islands in the western Atleutian Arc mimic those of the shallow continental shelf of the eastern Bering Sea to the extent that the marine community, including assemblages of forage fishes and their avian predators, has disinctly coastal characteristics. In contrast, marine avifauna and their prey at neighbouring Buldir Island are distinctly oceanic. For example, at the Near Islands, the ratio of thick-billed to common murres, Uria lomvia and U. aalge, is low and black.legged kittiwakes, Rissa tridacytla, but not red-legged kittiwakes, R. brevirostris, nest there. Diets of murres and kittiwkaes are dominated by sand lance, Ammodytes hexapterus, an abundant coastal species. At Buldir Island, thick-billed murres greatly outnumber common murres, red-legged kittiwakes and black-legged kittiwakes are both abundant, and diets of the birds consist primarily of oceanic squid and lantern-fish (Myctophidae). This mesoscale difference in food webs is apparently a consequence of the local physiography. A broad escarpment on the Near physiographic block creates a comparatively expansive, shallow, shelf-like habitat around the Near Islands, where a pelagic community typical of coastal regions flourished. Buldir Island is the only emergent feature of the Buldir physiographic block, with little shallow water surrounding it and, apparently, little opportunity for other than oceanic species to exist. Patterns in the distribution of fishes, and thus of sea birds, throughout the Atleutian Islands might be largely explained by the relationship between physical environments and food webs. In the larger context of fisheries oceanography, this model for the Aleutian Islands improves our ability to interpret physical and biological heterogeneity in the ocean and its relationship to regional community dynamics and trends in the abundance and productivity of individual species at higher tropic levels.