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: 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 this study, the impact of oceanic data assimilation on ENSO simulations and predictions is investigated. The authors’ main objective is to compare the impact of the assimilation of sea level observations and three-dimensional temperature measurements relative to each other. Three experiments were performed. In a control run the ocean model was forced with observed winds only, and in two assimilation runs three-dimensional temperatures and sea levels were assimilated one by one. The root-mean-square differences between the model solution and observations were computed and heat content anomalies of the upper 275 m compared to each other. Three ensembles of ENSO forecasts were performed additionally to investigate the impact of data assimilation on ENSO predictions. In a control ensemble a hybrid coupled ocean–atmosphere model was initialized with observed winds only, while either three-dimensional temperatures or sea level data were assimilated during the initialization phase in two additional forecast ensembles. The predicted sea surface temperature anomalies were averaged over the eastern equatorial Pacific and compared to observations. Two different objective skill measures were computed to evaluate the impact of data assimilation on ENSO forecasts. The authors’ experiments indicate that sea level observations contain useful information and that this information can be inserted successfully into an oceanic general circulation model. It is inferred from the forecast ensembles that the benefit of sea level and temperature assimilation is comparable. However, the positive impact of sea level assimilation could be shown more clearly when the forecasted temperature differences rather than the temperature anomalies themselves were compared with observations.

Description: The seasonal cycle over the tropical Pacific simulated by 11 coupled ocean–atmosphere general circulation models (GCMs) is examined. Each model consists of a high-resolution ocean GCM of either the tropical Pacific or near-global means coupled to a moderate- or high-resolution atmospheric GCM, without the use of flux correction. The seasonal behavior of sea surface temperature (SST) and eastern Pacific rainfall is presented for each model. The results show that current state-of-the-art coupled GCMs share important successes and troublesome systematic errors. All 11 models are able to simulate the mean zonal gradient in SST at the equator over the central Pacific. The simulated equatorial cold tongue generally tends to be too strong, too narrow, and extend too far west. SSTs are generally too warm in a broad region west of Peru and in a band near 10°S. This is accompanied in some models by a double intertropical convergence zone (ITCZ) straddling the equator over the eastern Pacific, and in others by an ITCZ that migrates across the equator with the seasons; neither behavior is realistic. There is considerable spread in the simulated seasonal cycles of equatorial SST in the eastern Pacific. Some simulations do capture the annual harmonic quite realistically, although the seasonal cold tongue tends to appear prematurely. Others overestimate the amplitude of the semiannual harmonic. Nonetheless, the results constitute a marked improvement over the simulations of only a few years ago when serious climate drift was still widespread and simulated zonal gradients of SST along the equator were often very weak.

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: 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: 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: 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: In this paper the performance of the global coupled general circulation model (CGCM) ECHO-2, which was integrated for 10 years without the application of flux correction, is described. Although the integration is rather short, strong and weak points of this CGCM can be clearly identified, especially in view of the model's performance of the annual cycle in the tropical Pacific. The latter is simulated with more success relative to the earlier version, ECHO-I. A better representation of the low-level stratus clouds in the atmosphere model associated with a reduction in the shortwave radiative flux at the air-sea interface improved the coupled model's performance in the southeastern tropical oceans, with a strongly reduced warm bias in these regions. Modifications in the atmospheric convection scheme also eliminated the AGCM's tendency to simulate a double ITCZ, and this behavior is maintained in the CGCM simulation. Finally, a new numerical scheme for active tracer advection in the ocean model strongly reduced the numerical mixing, which seems to enhance considerably the level of interannual variability in the equatorial Pacific. One weak point is an overall cold bias in the Tropics and midlatitudes, which typically amounts to 1°C in open ocean regions. Another weak point is the still too strong equatorial cold tongue, which penetrates too far into the western equatorial Pacific. Although this model deficiency is not as pronounced as in ECHO-1, the too strong cold tongue reduces the level of interannual rainfall variability in the western and central equatorial Pacific. Finally, the interannual fluctuations in equatorial Pacific sea surface temperatures (SSTs) are too equatorially trapped, a problem that is also found in ocean-only simulations. Overall, however, the authors believe that the ECHO-2 CGCM has been considerably improved relative to ECHO-1.