Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

Seepage and consolidation of bentonite saturated with pure- or salt-water by the method of unified molecular dynamics and homogenization analysis

Bentonite clay is a micro-inhomogeneous material, which consists of clay minerals (mainly montmorillonite), macro-grains (mainly quartz), water, air and others. Properties of the saturated bentonite clay are essentially characterized by the montmorillonite and water (i.e. montmorillonite hydrate). We analyze the molecular behavior of sodium montmorillonite hydrate Na_1/3Al₂[Si_11/3Al_1/3]O₁₀(OH)₂·nH₂O by applying a molecular dynamics (MD) simulation method. And by using the MD results we calculate the swelling property of the montmorillonite hydrate, and compare with an experimental result. Next, by using the same MD procedure we treat a montmorillonite mineral with a large number of external water molecules to check the properties of the water. Here we treat pure- and salt-water. Then we calculate the diffusivity and viscosity of water molecules and Na⁺ and Cl⁻ ions.

For extending the microscopic characteristics of constituent materials to a macroscopic seepage behavior of the micro-inhomogeneous material we apply a homogenization analysis (HA). That is, starting with the Navier–Stokes equation with distributed viscosity that is calculated by the former MD procedure we determine macroscopic permeability characteristics of bentonite for both cases of pure- and salt-water. Then, by using the permeability property we calculate long-term consolidation behavior of buffering clay, which is planed to be used for high-level radioactive waste (HLRW) management. Here the deformation is treated under the well-defined Cam clay model.     

Mid-chain ketocarboxylic acids in the remote marine atmosphere: Distribution patterns and possible formation mechanisms

In remote marine aerosol samples collected from the North Pacific ocean, Enewetak Atoll, American Samoa, and New Zealand, series of mid-chain ketocarboxylic acids in the range of C₆-C₁₈ were detected. All the positional isomers, except for the 2-oxo and 3-oxo species, were detected for major ketoacid families (e.g. C₉, C₁₁ and C₁₃). Higher ketoacid concentrations (up to 19 ng/m³) were obtained in the northern North Pacific aerosol samples, which generally showed an odd carbon-numbered predominance with 5-oxoundecanoic acid being the major species. By contrast, lower concentrations were obtained in the lower-latitude or subtropical aerosol samples, where even carbon-numbered ketoacids were relatively abundant.The distribution patterns of the odd carbon-numbered ketoacids could not be explained by the primary emissions from source materials including terrestrial higher plants, soil particles, and ocean surfaces. We consider that the isomeric ketocarboxylic acids are produced in the atmosphere by the photochemical oxidation of semi-volatile monocarboxylic acids, which are counterparts of the oxidative degradation of unsaturated fatty acids emitted from seawater surfaces. Atmospheric production of the ketoacids is seemingly enhanced in the northern North Pacific, probably due to an enhanced primary productivity.     

Seasonal Variation of Stratification in the Gulf of Thailand

Intensive hydrographic observations were carried out in the western part of the Gulf of Thailand and the east coastal sea of Peninsular Malaysia in September 1995 and April–May 1996. The characteristics of seasonal variation of oceanic condition in that area are discussed basis of an analysis of observed water temperature, salinity and density distributions in these cruises and NAGA cruises (Yanagi and Takao, 1998a). Stratification is most developed in March–May mainly due to large sea surface heating and weak sea surface wind, which weakened until September–October, vanishing in December–January. The horizontal distribution of bottom cold, saline and heavy water masses, which are found during the stratified season, is governed by the tidal mixing and the water depth. Water exchange between the Gulf of Thailand and the South China Sea becomes large in March–May due to a coupled effect of the intensified estuarine circulation and the Ekman transport by the southwest monsoon. This revised version was published online in August 2006 with corrections to the Cover Date.     

The reversible effect of temperature on the chemical composition of interstitial water of marine sediment

The reversibility of the temperature effect on the chemical composition of interstitial waters of three deep-sea sediment samples was examined between 2 and 25°C for Cl, Na, K, Mg, Ca, Si, B, Mn and alkalinity. When the temperature of sediment samples was returned from 25°C to the initial value of 2°C, most chemical species gave nearly their initial concentrations. However, for alkalinity and in one case for magnesium, it took another three to four hours to reach their initial concentrations.     

Interannual variability and predictability of summertime significant wave heights in the western north pacific

We propose and validate a linear regression model which enables us to predict the summer (June–August) mean of the monthly 90th percentile of significant wave heights (H₉₀) in the western North Pacific (WNP). The most prevailing interannual variability of H⁹⁰ is identified by applying an Empirical Orthogonal Function analysis to H⁹⁰ obtained from the ERA-40 wave reanalysis as well as from the optimally interpolated TOPEX/Poseidon (OITP) wave data. It is found that the increase of H⁹⁰ is correlated with cyclonic circulation in the WNP which links with warm SST anomalies in the Niño-3.4 region. We adopt zonal wind anomaly averaged over the region 5°N–15°N, 130°E–160°E (U^10N) as a predictor of the first principal component (PC1) of H⁹⁰, since U^10N is closely correlated with the PC1 of H⁹⁰. It is revealed that regression models obtained from two different wave datasets are nearly identical. The predictability of the regression model is assessed in terms of the reduction of the root-mean-square (rms) errors between H⁹⁰ and the reconstructed data. The predictor is found to be successful in reducing the rms errors by up to 40% for the ERA-40 wave reanalysis and by up to 70% for the OITP wave data within the latitudinal band 10°N–25°N, though rms errors exceeding 0.3 m still remain, particularly in the East China Sea.     

Accuracies of NOAA/NESDIS sea surface temperature estimation technique in the oceans around Japan

We have examined accuracies of nine nighttime National Oceanic and Atmospheric Administration/National Environmental Satellite, Data and Information Service (NOAA/NESDIS) equations for SST estimation using the Advanced Very High Resolution Radiometer (AVHRR)/NOAA-11 dataset produced by Sakaida and Kawamura (1992). Among the nine equations, the revised triple-window CPSST algorithm gives the smallest rms error, which is 0.38°C. The dual-window MCSST algorithm gives the largest rms error 0.56°C. Rms errors of the other algorithms are smaller than 0.5°C.     

Origin of theAbiki phenomenon (a kind of seiche) in Nagasaki Bay

Large oscillations of water level in Nagasaki Bay are calledAbiki and are most frequently observed in winter. The largestAbiki recorded in the past 20 years at the tide station at Nagasaki occurred on March 31, 1979. Simultaneously, a distinct atmospheric pressure disturbance of solitary type with an amplitude of about 3 mb was recorded at several neighbouring stations in Kyûshû, which indicated the pressure disturbance probably travelled eastward with an average speed of about 110 km h^–1.The quantitative relation between this pressure disturbance and notable seiches observed in Nagasaki Bay is examined by means of numerical simulation, and it is confirmed that the exceptionally large range of oscillations in the bay, which reached 278 cm at the tide station, was indeed produced by this travelling pressure disturbance.The leading part of shallow water waves induced by the atmospheric pressure disturbance was amplified up to about 10 cm in amplitude, over the broad continental shelf region off China, because of near resonant coupling to the pressure disturbance. After leaving this continental shelf region, the amplified water wave converged into the shelf region (Gotô Nada) surrounded by the north-western coast of Kyûshû and the Gotô Islands and excited eigenoscillations on the shelf. A train of waves thus formed with a period of about 35 min entered Nagasaki Bay and was resonantly amplified at periods of 36 min and 23 min which are the eigen periods of the bay. Besides resonance, the combined effects of shoaling and reflection inside Nagasaki Bay also enhanced the amplification.     

Seasonal Variation of Space/Time Statistics of Short-Term Sea Surface Temperature Variability in the Kuroshio Region

Spatial and temporal scales of sea surface temperature (SST) variations in the Kuroshio region have been investigated using a satellite-based one-year merged SST product. Targeting short-term variations with temporal scales of less than a year, decorrelation scales, which are defined as the e-folding scale of SST variability, have been derived as functions of regional positions and calendar months. We assumed that the autocorrelation function of SST has anisotropic Gaussian characteristics in the space-time domain. Resultant spatial and temporal decorrelation scales range from 1 to 3° and 2 to 3 days, respectively. They are strongly inhomogeneous, anisotropic and time-dependent. These characteristics are attributed to the oceanic and atmospheric disturbances. Spatial decorrelation scales are determined mainly by strong atmospheric forcing in the study region. In the area with dominant atmospheric forcing, the spatial scales are larger than those in the other regions. Those in the regions with dynamical oceanographic disturbances are as small as 1°. Signal-to-noise ratios are also large where the atmospheric forcing is strong, while they are small where the oceanic signals are active.     

Statistical study on the local equilibrium between wind and wind waves by using data from ocean data buoy stations

The local equilibrium between the wind and wind waves, which is defined by a range of the coefficient of the 3/2-power law between the non-dimensional significant wave height and period, is statistically investigated by using wind and wave data obtained at four ocean data buoy stations in the seas near Japan. The friction velocity is calculated from the wind speed measured at one height together with the significant wave period by using formulas of the wave dependent drag coefficient proposed by Tobaet al. (1990). The data for small waves or for weak winds indicate that the waves do not satisfy the criterion for the local equilibrium, because they may be affected by changing winds or remotely generated swells. In the seas near Japan, the data which satisfy the local equilibrium are about 6% through a year. Otherwise swells are dominant in most situations. Changing winds also cause deviations from the local equilibrium. The degree of satisfaction of the local equilibrium can be classified by ranges of the significant wave height. As the significant wave height exceeds 4 m, the local equilibrium is more frequently satisfied.