The high-pressure C2/c–P21/c phase transition along the LiAlSi2O6–LiGaSi2O6 solid solution

Two synthetic single-crystals with composition Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆ and space group C2/c at room conditions have been studied under pressure by means of X-ray diffraction using a diamond anvil cell. The unit-cell parameters were determined at 12 and 10 different pressures up to P = 8.849 and P = 7.320 GPa for Li(Al_0.53Ga_0.47)Si₂O₆ and LiGaSi₂O₆, respectively. The sample with mixed composition shows a C2/c to P2₁/c phase transformation between 1.814 and 2.156 GPa, first-order in character. The transition is characterised by a large and discontinuous decrease in the unit-cell volume and by the appearance of the b-type reflections (h + k = odd) typical of the primitive symmetry. The Ga end-member shows the same C2/c to P2₁/c transformation at a pressure between 0.0001 and 0.39 GPa. The low-pressure value at which the transition occurred did not allow collecting any data in the C2/c pressure stability field except that on room pressure. Our results compared with those relative to spodumene (LiAlSi₂O₆, Arlt and Angel 2000a) indicate that the substitution of Al for Ga at the M1 site of Li-clinopyroxenes strongly affects the transition pressure causing a decrease from 3.17 GPa (spodumene) to less than 0.39 GPa (LiGaSi₂O₆) and decreases the volume discontinuity at the transition. As already found for other compounds, the C2/c low-pressure phases are more rigid than the P2₁ /c high-pressure ones. Moreover, the increase of the M1 cation radius causes a decrease in the bulk modulus K _T0. The axial compressibility among the Li-bearing clinopyroxenes indicates that the c axis is the most rigid for the C2/c phases while it becomes the most compressible for the P2₁ /c phases.     

Long-term change in the status of water pollution in Tokyo Bay: recent trend of increasing bottom-water dissolved oxygen concentrations

Journal of Oceanography - Long-term trends of bottom-water concentrations of dissolved oxygen (DO), total nitrogen, and total phosphorus at 42 sites in Tokyo Bay were analyzed using monthly data...     

A type of second order linear ordinary differential equations with periodic coefficients for which the characteristic exponents have exact expressions

It is shown that the characteristic exponents can be exactly expressed for a type of second order linear ordinary differential equations with periodic coefficients (Hill's equation) which appear as the variational equations of certain periodic solutions of dynamical systems. Key points are the transformation of the equation to the Gauss' hypergeometric differential equation, and evaluation of the trace of monodormy matrix in the complex plane of the independent variable. Two simple examples are given for which the stability of periodic solutions is rigorously analyzed.     

High-resolution observations of solar radio bursts with multi-element compound interferometers at 3.75 and 9.4 GHz

High-resolution observations of solar radio bursts made simultaneously with multi-element compound interferometers at 3.75 and 9.4 GHz are presented.Preliminary results are: (1) The burst of December 16, 1967 showed a change in polarization distribution in the radio source, which suggests a magnetic field change in the source. (2) The existence of the multi-source burst is also confirmed at 3.75 GHz. (3) The source size of the impulsive burst is estimated to be 0.'5. (4) Among the GRF bursts there seem to be two kinds; one has a large angular size and the other has a small one.A brief discussion is given of the burst of December 16, 1967.     

Comparison of surface velocities determined from altimeter and drifting buoy data

Surface velocities determined from trajectory of a drifting buoy from March through November 1987 are compared with surface geostrophic velocities determined from sea surface dynamic topography (SSDT) obtained from altimetry data with the aid of long-term hydrographic observation data. In general, these velocities show similar temporal variations in both zonal and meridional components, except in a period when obvious error is found in the altimetric SSDT field. When the buoy was trapped by several mid-ocean meso-scale eddies, the comparison is especially good. Systematic discrepancy is found, however, when the buoy was in the Kuroshio region, because of using both temporally and spatially smoothed mean SSDT estimated from hydrographic data; instead, surface geostrophic velocities determined from the altimetric SSDT referred to the improved geoid model result in better comparison.     

Spin-up and spin-down processes of the large cold water mass of the Kuroshio south of Japan

Time variation of the cold water mass of the Kuroshio south of Japan, which was formed in August 1975 and disappeared in August 1980, is studied. Its lifecycle includes several repetitions of spin-down and spin-up processes. The spin-down (or the spin-up) process is accompanied by warming (cooling) of the cold water mass and descending (ascending) motion of the inner water. Expansion of the cold water area is also associated with the spin-up period while shrinking occurs in the spin-down period. The rate of spin-down of the cold water mass is approximately equal to that of the Gulf Stream rings. The spin-up process is not observed in the Gulf Stream rings and the longer lifetime of the cold water mass off Japan, in comparison with the Gulf Stream rings, is due to the existence of the spin-up periods. The spin-up process tends to occur in late spring to summer, and it seems to be related to the seasonal variation in intensity of the Kuroshio.     

Mantle hydrocarbons: abiotic or biotic?

Analyses of 227 rocks from fifty localities throughout the world showed that mantle derived rocks such as tectonized peridotites in ophiolite sequences (tectonites) arid peridotite xenoliths in alkali basalts contain heavier hydrocarbons (n-alkanes), whereas igneous rocks produced by magmas such as gabbro arid granite lack them. The occurrence of hydrocarbons indicates that they were not derived either from laboratory contamination or from held contamination; these compounds found in the mantle-derived rocks are called here "mantle hydrocarbons." The existence of hydrocarbons correlates with petrogenesis. For example, peridotite cumulates produced by magmatic differentiation lack hydrocarbons whereas peridotite xenoliths derived from the mantle contain them. Gas chromatographic-mass spectrometric records of the mantle hydrocarbons resemble those of aliphatics in meteorites and in petroleum. Features of the hydrocarbons are that (a) the mantle hydrocarbons reside mainly along grain boundaries and in fluid inclusions of minerals; (b) heavier isoprenoids such as pristane and phytane are present; and (c) delta 13C of the mantle hydrocarbons is uniform (about -27%). Possible origins for the mantle hydrocarbons are as follows. (1) They were in organically synthesized by Fischer-Tropsch type reaction in the mantle. (2) They were delivered by meteorites and comets to the early Earth. (3) They were recycled by subduction. The mantle hydrocarbons in the cases of (1) and (2) are abiogenic and those in (3) are mainly biogenic. It appears that hydrocarbons may survive high pressures and temperatures in the mantle, but they are decomposed into lighter hydrocarbon gases such as CH4 at lower pressures when magmas intrude into the crust; consequently, peridotite cumulates do not contain heavier hydrocarbons but possess hydrocarbon gases up to C4H10.     

Deposition rates of polysilicic acid with up to 10 M calcium ions

Cementitious materials used for radioactive waste repository construction complicate the performance assessment of radioactive waste systems because the use of cement may greatly alter the pH (8–13) of groundwater and release constituents such as calcium ions. Under such conditions, it is important to clarify also the dynamic behavior of silica (silicic acid), in order to evaluate the alteration in the chemical and physical properties of the fractured layer or the host rock surrounding the repository. Since silica undergoes polymerization, precipitation or dissolution depending on the pH and/or temperature, the behavior of silica would be greatly complicated in the presence of other ions. This study is focused on the deposition rates of polysilicic acid and soluble silicic acid with up to 10⁻³ M Ca ions. In the experiment, Na₂SiO₃ solution (250 mL, pH > 10, 298 K) was poured into a polyethylene vessel containing amorphous silica powder (0.5 g), and a buffer solution, HNO₃, and CaNO₃ as Ca ions were sequentially added into the vessel. The pH of the solution was set to 8. The silica, initially in a soluble form at pH > 10 (1.4 × 10⁻² M), became supersaturated and either deposited on the solid surface or changed into the polymeric form. Then the concentrations of both poly- and soluble silicic acid were monitored over a 40-day period. The decrease of polysilicic acid became slow with an increase in the concentration of Ca ions in the range of up to 10⁻³ M. In general, the addition of electrolytes to a supersaturated solution accelerates the aggregation and precipitation of polymeric species. However, the experimental result showed that polysilicic acid in the presence of Ca ions is apparently stable in solution, compared with that under a Ca-free condition. On the other hand, the concentration of soluble silicic acid in the presence of Ca ions immediately became metastable, that is, slightly higher than the solubility of soluble silicic acid. Its dynamic behavior was similar to that in the Ca-free condition.     

Active strike–slip faulting and macroscopically nonrigid deformation of volcanic rocks in central Japan inferred from a paleomagnetic study

Detailed paleomagnetic investigation of a pyroclastic flow deposit has clarified the deformation mode around an active fault. In central Japan, the early Quaternary Nyukawa Pyroclastic Flow Deposit is cut by the active dextral Enako fault. Activity level of the fault is evaluated on the basis of geological and geomorphological surveys. Then, paleomagnetic samples are collected from 22 sites at exposures located on a lineament that is adjoining and parallel to the Enako fault. Stable thermoremanent magnetization (TRM) of the pyroclastic deposit is isolated through progressive thermal and/or alternating field demagnetization tests. Untilted site-mean directions of the TRMs simultaneously acquired during initial cooling indicate significant clockwise vertical-axis rotation. The lineament was then activated with right-lateral motions through the early Quaternary. Together with the late Quaternary activities along the adjoining Enako fault evaluated by our study, the present result exemplifies a migration of active segments within a fault system during the Quaternary. Paleomagnetic directions on the strike–slip fault are not concordant with uniform deformation predicted by the model of rotation of rigid blocks aligned on a master fault, but suggestive of a periodic deformation as a result of intense fracturing and differential rotation of blocks bounded by nested parallel faults.     

The crystal structure of CaFe3+SiAlO6 and the crystal chemistry of Fe3+—Al3+ substitution in calcium Tschermak's pyroxene

The crystal structure of a synthetic CaFe³⁺Al-SiO₆ pyroxene (20 kb, 1,375° C) with unit cell dimensions a=9.7797(16), b=8.7819(14), c=5.3685(5) Å, =105.78(1), space group C2/c has been refined by the method of least squares to an R-factor of 0.025 based on 812 reflections measured on an automatic single crystal diffractometer. The octahedral M1 site is occupied by 0.82 Fe³⁺ and 0.18 Al³⁺. Within the tetrahedral T site, Si⁴⁺ (0.50), Al³⁺ (0.41) and Fe³⁺ (0.09) ions are completely disordered, although submicroscopic domains with short-range order are very likely. The octahedral site preference energy of the Fe³⁺ ions with respect to Al³⁺ ions in CaFe³⁺AlSiO₆ is about 10 kcal/mole, which is much higher than that found in Y₃Al _x Fe_5–2O₁₂ garnets. Topologically the structure of CaFe³⁺AlSiO₆ is intermediate between that of diopside and calcium Tschermak's pyroxene, CaAlAlSiO₆. For CaM³⁺ AlSiO₆ clinopyroxenes an increase in the size of the M1 octahedron is accompanied by an increase in the average M2-0, bridging T-0 and 03-03 distances and kinking of the tetrahedral chain.