Spatial and Temporal Variation of Surface xCO<Subscript>2</Subscript> Providing Net Biological Productivities in the Western North Pacific in June

More than 14,000 measurements of surface water xCO₂ were obtained during two cruises, 3 weeks apart in June 2000, along 155°E between 34 and 44°N in the western North Pacific Ocean. Based on the distributions of salinity and sea surface temperature (SST), the region has been divided into 6 subregions; Oyashio, Oyashio front, Transition, Kuroshio front, and Kuroshio extension I and II zones, from north to south. The surface waters were always undersaturated with respect to atmospheric CO₂. The Oyashio water was the least undersaturated: its xCO₂ decreased slightly by 7 ppm, while SST increased by 2°C. The xCO₂ normalized to a constant temperature decreased considerably. In the two frontal zones, a large drawdown of 30–40 ppm was observed after 18–19 days. In the Kuroshio extension zones, the xCO₂ increased, but the normalized xCO₂ decreased considerably. The Transition zone water may be somewhat affected by mixing with the subsurface water, as indicated by the smallest SST rise, an undecreased PO₄ concentration, and a colder and less stable surface layer than the Oyashio front water. As the uncertainty derived from the air-sea CO₂ flux was not large, the xCO₂ data allowed us to calculate the net biological productivity. The productivities around 60 mmol C m⁻²d⁻¹ outside the Transition zone indicate that the northwestern North Pacific, especially the two frontal zones, can be regarded as one of the most productive oceans in the world.     

High temperature X-ray study of single crystal stishovite synthesized with Li2WO4 as flux

Single crystal stishovite with a square prismatic habit and maximum length 0.8 mm was grown from α-quartz at 120 kbar and ～1,300° C. Li₂WO₄, chosen as a result of a previous experiment in growing coesite, was also successful as flux for stishovite. Single crystal X-ray structure analysis of the crystals thus obtained has been carried out at high temperatures under ambient pressure. Lattice constant measurements give a larger thermal expansion coefficient along the a-axis than along the c-axis. The bond distances and bond angles show a decreasing distortion of the SiO₆ octahedron with increasing temperature. The increasing amplitude of thermal vibrations of oxygen atoms with increasing temperature results in increasing O-O repulsion in the basal plane, which explains the observed crystallographic changes.     

Local structure of (Ca, Sr)2 (Mg, Co, Zn) Si2O7 melilite solid-solution with modulated structure

The local structure around Co, Zn and Sr atoms in incommensurately modulated, melilite-type X₂T¹ T ₂ ² O₇ (X=Ca and Sr, T¹=Mg, Co and Zn, T²=Si) solid-solutions has been investigated by EXAFS analyses. The modulated structure was confirmed in Ca_2-xSr_xCoSi₂O₇ solid-solutions with X=0.0 to 0.6 and for both Ca₂Mg_1-YCo_YSi₂O₇ and Ca₂Mg_1-YZn_YSi₂O₇ solid-solutions over the whole compositional range at room temperature. The actual bond-distances determined by the EXAFS method for the T¹ site (Co-, Zn-O) in the modulated structure are longer than the mean bond-distances obtained from the X-ray diffraction method. This is attributable to the libration of the T¹ tetrahedra. In the Ca_1-XSr_XCoSi₂O₇ solid-solution both the Sr-O and Co-O distances by the EXAFS method for the X-site increase from Ca end-member to Sr end-member. These increases are respectively 0.8% and 0.6%. This means the local expansions of the tetrahedral sheets and of the XO polyhedra are well matched. In the modulated Ca₂Co_1-YMg_YSi₂O₇ and Ca₂Zn_1-YMg_YSi₂O₇ solid-solutions, the actual Co-O and Zn-O distances for the T¹-sites are nearly constant in the whole compositional range. The compositional variations of the local structure around the cations in the solid-solution are different for the X and T¹ sites. It is concluded that the local geometric restriction for the size of substituted cation in X site is larger than that in T¹ site. The dimension of the tetrahedral sheet puts restriction on the size of the cations situated at the interlayer X sites. In other words, the different behavior of the local geometric restriction between the X and T¹ sites is an important feature of the melilite structure and is also related to the modulated structure.     

Characterization of the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses

X-ray absorption spectroscopy using synchrotron radiation has been applied to the investigation of the coordination geometries around Y, Zr and Nb atoms in metamict zircon, gadolinite, fergusonite, euxenite and samarskite. EXAFS and XANES spectra of their crystalline counterparts and synthetic compounds including ZrO₂, Y₂O₃, YNbTiO₆, YNbO₄, LiNbO₃, and NiNb₂O₆ were also measured for comparison. Metamict zircon shows a significant decrease in its Zr-O bond distances accompanying an increase in distortion of the Zr-O coordination polyhedra as compared with crystalline zircon. On the contrary, the average Nb-O bond distances and the symmetry of the coordination polyhedra around the Nb atoms in metamict euxenite and samarskite resemble those in the crystalline euxenite. Compared with crystalline fergusonite, a decrease in the distortion of the Nb-O octahedra is observed in metamict fergusonite. The structures of the second nearest neighbors (the metal-metal interactions) are largely disrupted in the metamict specimens except for metamict zircon and samarskite with high trivalent iron concentration. Nb in metamict samarskite is in octahedral coordination by oxygen and is similar to that in euxenite.