Structure and dynamics of water on muscovite mica surfaces

The structure and dynamics of water on muscovite mica (0 0 1) surfaces have been investigated by molecular dynamics simulations. X-ray reflectivity profiles highly reflecting the interfacial structure are directly calculated and compared with those of experiments. The direct comparison has validated the usefulness of MD simulations to understand the real interfacial structure of the mica−water system. We observed five distinguished peaks in the density profile of oxygen present in water, and these peaks are attributable to the water molecules directly adsorbed on mica, hydrated to the K⁺ ions on the mica surface, and ordered due to hydrogen bonds between hydrated K⁺ ions. The hydrated K⁺ ions make an inner-sphere complex and have an explicit first hydration shell with a radius of 3.6 Å and a hydration number of 2.9. The change of the viscosity of water located above 1 nm apart from the mica surface was not observed. This feature is in good agreement with a recent experimental study in which the shear measurement was conducted using a surface forces apparatus. The increase of the viscosity by a factor of ca. 2-3 relative to that of the bulk water was observed at water located within 1 nm from the isolated mica surface.     

Variation of the partial pressure of CO2 in surface water from Kuroshio to Oyashio and the relation between environmental factors and the partial pressure at 144°E off Sanriku, northwestern North Pacific in May, 1997

Partial pressure of CO₂ in surface sea water (pCO₂) was measured continuously off Sanriku in May, 1997 by a new pCO₂ measurement system. We have examined the relation of pCO₂ to physical factors such as temperature, salinity and density, chemical and biological factors such as nutrients and carbonate system and chlorophylla. In the Kuroshio region pCO₂ was not correlated to physical, chemical and biological factors in the range of 260 to 290 μatom. In transition water (Tr1) between Kuroshio and the Oyashio second branch, pCO₂ was weakly correlated to physical factors and strongly correlated to nutrients. In transition water (Tr2) between the Oyashio first and second branches, pCO₂ was highly correlated to temperature (SD: 10.9 μatom) and salinity (SD: 8.6 μatom) and also to nutrients. In transition water (Tr1+Tr2), pCO₂ was highly multivariately correlated to temperature (T), salinity (S), chlorophylla (CH) (or nitrate+nitrite (N)) as follows, pCO₂(μatom)= 10.8×T(°C)+27.7×S+2.57CH(μg/1) −769, R²= 0.86, SD = 20.9, or pCO₂(μatom)= 3.9×T(°C)+25.5×S+16.0NO₃(μM) −686, R²= 0.99, SD = 6.4. Moreover, pCO₂ was predicted by only two factors, one physical (S) and the other chemical/biological (N) as follows: pCO₂ (μatom)=32.8×S+19.4N−908, R²=0.97, SD=8.4. The pH measured at 25°C was well correlated with normalized pCO₂ at a fixed temperature. In the Oyashio region pCO₂ was decreased to 160 μatom, probably because of spring bloom, but was not correlated linearly to chlorophylla. The results obtained showed the possibility of estimating pCO₂ of the Oyashio and transition regions in May by satellite remote sensing of SST, but the problem of estimation of pCO₂ in Kuroshio water remains to be solved.     

Kinetics of nitrate and ammonium uptake by the natural populations of marine phytoplankton in the surface water of the Oyashio region during spring and summer

The maximum uptake rate (_max) and affinity constant (K _s) for nitrate and ammonium were estimated in the surface water of offshore Oyashio in May (spring) and September (summer), 1990. The average _max/Chl.a for ammonium was 2.1 times larger than that of nitrate in both seasons. The average _max/Chl.a for both nitrogens were 3.5 times larger in summer than in spring. Water temperature and size composition of phytoplankton population were related to the seasonal difference in the _max/Chl.a. Phytoplankton population showed high affinity for both nitrogens in the spring and summer. In addition, the contribution of new production to total production was estimated by _max[_max–No₃/(_max–NO₃+_max–NH₄)]. The spring value was in the range of 0.26 to 0.45 (mean±SD=0.35±0.092), and the values in spring bloom were especially a little over 0.4. The summer value was in the range of 0.30 to 0.37 (0.34±0.04).     

Seasonal and Interannual Variation of DIC in Surface Mixed Layer in the Oyashio Region: A Climatological View

Eight-year observation results of DIC from 1996 to 2003 in the Oyashio region have been analyzed to obtain a climatological view of its seasonal variation and interannual variation. Data of DIC obtained by several institutes are synthesized to give a dataset with an uncertainty lower than 5 μmol/kg. The obtained climatology of NDIC seasonal variation in the Oyashio mixed layer shows a seasonal amplitude of 176 μmol/kg, with a maximum in January and a minimum in September. These features closely resemble those observed in the southern half of the western subarctic North Pacific (WSNP) including Station KNOT, although the timing of the NDIC maximum is slightly advanced in the case of the Oyashio. Analysis using a quasi-conservative tracer Cp0 (NDIC - 106NP) shows that among 176 μmol/kg of NDIC seasonal variation, only 16 μmol/kg is attributed to hydrographic processes while the remaining 160 μmol/kg is attributed to biological processes. The Cp0 value in the Oyashio mixed layer also resembles that of the WSNP mixed layer during the months May to November, suggesting further resemblance of the Oyashio water mass to that of WSNP in terms of carbon dynamics. The present results also suggest that a single data obtained in Oyashio mixed layer contains 30 μmol/kg of potential uncertainty for the representativity of this region, which leads to a note about a need to treat with caution results obtained by a single observation in this region.     

Multi‐species diffusion analysis in porous media under various dry density and temperature conditions: molecular dynamics simulation,homogenization analysis,and finite element method

In porous media, chemical species that dissolve in pore water can be transported via diffusion mechanisms or advective fluxes, close to or far away from where precipitation occurs. In the case of a high‐level radioactive waste disposal system, compacted bentonite is used in a buffer material in an engineering barrier system to minimize the amount of specific nuclides that breach into the surrounding host rock. To minimize breaching, it is very important to understand the transport mechanism of multiple chemical species in porous media. In the following research, we introduced FEM analysis methods using the results of the molecular dynamics simulation and homogenization analysis (MD/HA) method. First, the diffusion coefficients of ions (Cl^?, I^?, and Na⁺) in different water layers of Na‐beidellite were calculated using the MD/HA procedure under various dry density (1.2, 1.6, and 2.0 Mg/m³) and temperature (293, 323, and 363 K) conditions. Next, using FEM analysis that used the MD/HA results as input parameters, the diffusion behaviors of ions in porous media were calculated. The results indicate that the diffusion coefficients of the interlayer water in Na‐beidellite are different from the diffusion coefficients under dry density conditions. Further, the concentration profiles (C_t/C₀) of iodine and chloride are proportional to temperature but inversely proportional to dry density. Copyright © 2014 John Wiley & Sons, Ltd.     

Transport phenomena in kaolinite clay: Molecular simulation,homogenization analysis and similitude law

Kaolinite is a common clay mineral. It is a nanomaterial with a platelet crystalline structure. In order to analyze the behavior of kaolinite, its microscopic structure and material properties must be specified correctly. A molecular dynamics (MD) simulation is used for determining the microscale properties of hydrated kaolinite, and these properties are introduced into a multiscale homogenization analysis (HA). We previously developed such an MD/HA technique to investigate seepage, diffusion, sorption and consolidation in bentonite clay (Proceedings of the Science Basis for Nuclear Waste Management, Davos, Switzerland, vol. XXI. Material Research Society: Warrendale, PA, 1997; 359–366; Eng. Geol. 1999; 54 :21–31; Eng. Geol. 2001; 60 :127–138; Coupled Thermo‐Hydro‐Mechanical‐Chemical Processes in Geo‐systems. Elsevier: Amsterdam, 2005; 457–464). We here apply the method to kaolinite clay to investigate the permeability, diffusion and related similitude law. The obtained results are supported by existing experimental data. Copyright © 2008 John Wiley & Sons, Ltd.     

Phylogeny and phylogeography of the land hermit crab Coenobita purpureus (Decapoda: Anomura: Coenobitidae) in the Northwestern Pacific Region

Hermit crabs of the family Coenobitidae comprise the land hermit crabs, with 16 Coenobita species, and the coconut crab Birgus latro. They are terrestrial but spend their marine life as planktonic larvae. Some coenobitid crabs are widely distributed in the Indo‐West Pacific region, and some species occupy narrower ranges. To improve our knowledge of coenobitid crab speciation and geographical distribution patterns, we examined the phylogenetic relationship between Coenobita purpureus, which has a narrow distribution in the Northwestern Pacific, and its more widely distributed coenobitids including B. latro, Coenobita brevimanus, Coenobita cavipes, Coenobita perlatus, Coenobita rugosus and Coenobita violascens based on the mtDNA cytochrome c oxidase subunit I (COI) and 16S rDNA genes. We also assessed the phylogeography of Co. purpureus populations based on the COI gene. Our phylogenetic and phylogeographical analyses revealed that (i) Co. purpureus clustered with Co. rugosus and (ii) the Co. purpureus population in the Ogasawara Islands was genetically distinct from those in other regions, which showed genetic panmixia. It has been hypothesized that Co. purpureus evolved in the isolated landmasses of the Ryukyu region during the Pliocene, and that its population expanded and colonized the Ogasawara Islands in the late Pleistocene. Further phylogeographical studies on Coenobita species with relatively narrow distributions coupled with characterization of their phylogenetic relationships with widely distributed congeners will advance our knowledge of the speciation and geographical distribution history of coenobitid crabs.     

Sequential Chemical Separation of Cr and Ti from a Single Digest for High‐Precision Isotope Measurements of Planetary Materials

Combined determination of Cr and Ti isotopes of planetary materials offers a means with which to investigate their genetic relationship and the evolution of the protoplanetary disk. Here, we report the new sequential chemical separation procedure for combined Cr and Ti isotope ratio measurements. It comprises three steps: (a) Fe removal using AG1‐X8 anion exchange resin, (b) Ti separation using TODGA resin and (c) Cr separation using AG50W‐X8 cation exchange resin (with one additional step of Ti purification using AG1‐X8 anion exchange resin for samples having high Cr/Ti and Ca/Ti ratios). We applied the proposed procedure to terrestrial and meteorite samples with various compositions. Typical recovery rates of 90–100% were achieved with total procedural Cr and Ti blanks of 3–5 and 2–3 ng, respectively. We measured the Cr and Ti isotope compositions of the separated samples using thermal ionisation mass spectrometry and multiple collector‐inductively coupled plasma‐mass spectrometry, respectively. Our Cr and Ti isotope data were found to be consistent with those of previous studies of individual Cr and Ti isotopic compositions of the meteorites. These results demonstrate the capability of our separation method when applied to combined high‐precision Cr and Ti isotope analyses for single digests of planetary materials.     

Magnitudes of large shallow earthquakes from 1904 to 1980

In order to obtain a uniform magnitude catalogue, surface-wave magnitudes M_s and broad-band body-wave magnitudes m_B have been determined for large shallow earthquakes from 1904 to 1980. In making the catalogue homogeneous, the author consistently adheres to the original definitions of M_s and m_B given by Gutenberg (1945) and Gutenberg and Richter (1956). The determinations of M_s and m_B are all based on the amplitude and period data listed in Gutenberg and Richter's unpublished notes, bulletins from stations worldwide, and other basic information. m_B is measured on broad-band instruments in periods of ～8 s. Consistency of the magnitude determinations from these different sources is carefully checked in detail. More than 900 shallow shocks of magnitude 7 and over are catalogued. The meaning of the magnitude scales in various catalogues is examined in terms of M_s and m_B. Most of the magnitudes listed by Gutenberg and Richter (1954) in their “Seismicity of the Earth” are basically M_s for large shocks shallower than 40 km, but are basically m_B for large shocks at depths of 40–60 km. The surface-wave magnitudes given by “Earthquake Data Reports” are higher than M_s by 0.2 unit whether the combined horizontal amplitude or the vertical amplitude is used. m_B and the currently used 1 s body-wave magnitude are measured at different periods and should not be directly compared.