High-pressure electronic absorption spectroscopy of natural and synthetic Cr<Superscript>3+</Superscript>-bearing clinopyroxenes

Comparison of polarized optical absorption spectra of natural Ca-rich diopsides and synthetic NaCrSi2O6 and LiCrSi2O6 clinopyroxenes, evidences as vivid similarities, as noticeable differences. The similarities reflect the fact that in all cases Cr3+ enters the small octahedral M1-site of the clinopyroxene structure. The differences are due to some iron content in the natural samples causing broad intense near infrared bands of electronic spin-allowed dd transitions of Fe2+(M1, M2) and intervalence Fe2+/Fe3+ charge-transfer transition, and by different symmetry and different local crystal fields strength of Cr3+ in the crystal structures. The positions of the spin-allowed bands of Cr3+, especially of the low energy one caused by the electronic 4 A 2g → 2 T 1g transition, are found to be in accordance with mean M1–O distances. The local relaxation parameter ε calculated for limCr 3+ → 0 from the spectra and interatomic á Cr - O ñ \left\langle {Cr - O} \right\rangle and á Mg - O ñ \left\langle {Mg - O} \right\rangle distances yields a very high value, 0.96, indicating that in the clinopyroxene structure the local lattice relaxation around the “guest” ion, Cr3+, deviates greatly from the “diffraction” value, ε = 0, than in any other known Cr3+-bearing systems studied so far. Under pressure the spin-allowed bands of Cr3+ shift to higher energies and decrease in intensity quite in accordance with the crystal field theoretical expectations, while the spin-forbidden absorption lines remain practically unshifted, but also undergo a strong weakening. There is no evident dependence of the Racah parameter B of Cr3+ reflecting the covalence of the oxygen-chromium bond under pressure: within the uncertainty of determination it may be regarded as practically constant. The values of CrO6 octahedral modulus, k\textpoly\textloc k_{\text{poly}}^{\text{loc}} , derived from high-pressure spectra of natural chromium diopside and synthetic NaCrSi2O6 kosmochlor are very close, ~203 and ~196 GPa, respectively, being, however, nearly twice higher than that of MgO6 octahedron in diopside, 105(4) GPa, obtained by Thompson and Downs (2008). Such a strong stiffening of the structural octahedron, i.e. twice higher value of k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} comparing with that of k\textMg2 + \textloc k_{{{\text{Mg}}^{2 + } }}^{\text{loc}} , may be caused by simultaneous substitution of Ca2+ by larger Na+ in the neighboring M2 sites at so-called jadeite-coupled substitution Mg2+ + Ca2+ → Cr3+ + Na+. It is also remarkable that the values of CrO6 octahedral modulus of NaCrSi2O6 kosmochlor obtained here are nearly twice larger than that of 90(16) GPa, evaluated by high-pressure X-ray structural refinement by Origlieri et al. (2003). Taking into account that the overall compressibility of the clinopyroxene structure should mainly be due to the compressibility of M1- and M2-sites, our k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} -value, ~196 GPa, looks much more consistent with the bulk modulus value, 134(1) GPa.     

Field measurement and modeling of near-bed sediment transport processes with fluid mud layer in Tokyo Bay

Tokyo Bay is one of the estuaries in Japan with a high population of almost 26 million people in the basin area. One of the major concerns for the environment in this water area is the decreasing ecosystem functions including the deterioration of water and sediment qualities caused by various anthropogenic activities. Since the bottom sediments around almost the entire area of the inner bay consist of fine materials with a high organic content, which cause the deterioration of water quality through processes such as hypoxia, an understanding of the fine sediment dynamics in the Bay is crucial for an environmental assessment of the water area. This paper proposes a model for the key processes of fine sediment dynamics, which reflects field data about muddy bed structures and their dynamics obtained during the monitoring campaign in 2007. One of the specific features of the sediment in the Bay at present is the persistent existence of fluid mud layers (water content over 300 %) with a thickness of around a few decimeters, which might be caused by deposition of abundant organic particles due to eutrophication. The present study shows that diffusion flux model delivers quite reliable results for estimating erosion flux from the top of fluid mud layers after calibrating the model parameter against the time series data of vertical flux measured by an acoustic Doppler velocimeter system. This study also derives analytical solutions, based on the Bingham fluid concept, of advection flux in the fluid mud layer on which external shear stress force is applied.

     

Observed and simulated sensitivities of summertime urban surface air temperatures to anthropogenic heat in downtown areas of two Japanese Major Cities,Tokyo and Osaka

In this study, the sensitivities of surface air temperatures to anthropogenic heat (AH) were investigated in downtowns of the two Japanese major cities, Tokyo and Osaka. First, meteorological measurements were made with the simultaneous monitoring of electricity demand in a contrastive couple of a downtown commercial area (C-area) and a residential area (R-area) within each city in summer 2007. From the measurements, the areal-mean surface air temperatures were obtained as \( {\overline{T}}_{\mathrm{C}} \) and \( {\overline{T}}_{\mathrm{R}} \) for each of the C-area and R-area, respectively. Using the actual electricity demand and the estimated motor fuels consumption, their areal total was evaluated as the energy-consumption-basis AH. The estimated C-areas' AH indicated greater values up to 220 W/m² on weekdays and remarkable decrease about by half on weekends, whereas that in the R-areas showed less values of 10–20 W/m² stably. Then, \( {\overline{T}}_{\mathrm{C}}-{\overline{T}}_{\mathrm{R}} \) on calm and fine days were found to be systematically decreased from weekdays to weekends in both cities roughly indicating a proportional relationship with the reductions in the C-areas' AH on weekends. The result suggested a common afternoon sensitivity for both C-areas of around 1.0°C/100 W/m², which indicated an intensity of the AH impact on surface air temperature there. Next, to simulate the observed AH impact, the authors' CM-BEM (a multilayer urban canopy model coupled with a building energy model) was newly implemented in the mesoscale Weather Research and Forecasting (WMF) model. This new system, WRF-CM-BEM, was applied to Tokyo and almost reasonably validated from the aspects of the reproducibility of urban surface air temperature and electricity demand in the observation areas. The simulations also suggested that WRF-CM-BEM underestimated the observed air temperature sensitivity to AH in the Tokyo C-area roughly by half but still in the same order of magnitude.     

A new derivation of the Kustaanheimo-Stiefel variables

First introducing the parabolic coordinates inR ³, we can derive the Kustaanheimo-Stiefel (KS) variables quite simply and naturally. Through this derivation it becomes clearer where and how the additional dimension is introduced and what the bilinear relation means.Paper presented at the 1981 Oberwolfach Conference on Mathematical Methods in Celestial Mechanics.This paper is dedicated to the 60th Birthday of Prof. V. Szebehely.     

Concentration of polychlorinated biphenyls (PCBs) in beached resin pellets: variability among individual particles and regional differences

Concentrations of polychlorinated biphenyls (PCBs) in beached resin pellets were examined to reveal variability between individual particles and differences among beaches. Fifty-five resin pellets from a beach in Tokyo were individually analyzed for PCBs, and showed concentrations ranging from <28 to 2,300 ng/g. This indicates that concentrations are highly variable between particles. Among several characters, discoloration (e.g., yellowing) had a positive relationship with PCB concentration: discolored pellets contained more PCBs than others on most of the beaches sampled. Given the color-selective ingestion of food by some organisms, this may be ecotoxicologically important. Measurements of samples from 47 beaches in Japan showed regional differences in PCB concentrations in resin pellets consistent with those in mussels. Sporadic high concentrations of PCBs were also found in pellets from remote islands, suggesting that resin pellets could be the dominant route of exposure to the contaminants at remote sites. The similarity of PCB concentrations between resin pellets and mussels suggests a potential use of resin pellets to monitor pollution in seawater.     

Process of slip-surface development and formation of slip-surface clay in landslides in Tertiary volcanic rocks, Japan

Once landslide movement has been initiated, the sliding mass tends to move toward a more stable position. However, landslides that have occurred in some Tertiary volcanic rocks in Japan show recurrent movement. A possible reason for this behavior is that the mineral composition and properties of slip-surface materials results in better ‘lubrication’ along the slip surface as movement continues. In order to determine the causes, five landslides in Japanese Tertiary volcanics with different movement histories were studied. Based on geological investigation, the results presented in this paper were obtained by studying the development process and formation of slip surfaces and clays in landslides in these volcanics.

For rocks of similar types and mineralogies the clay content of slip-surface materials can be directly related to the displacement and history of slide movement. This study indicates that the type of slip surface ranges from: (1) striation type (showing only striations on bedrock without clay), to (2) brecciated type (clayey breccia), (3) mylonite type (clay with breccia), and to (4) clay type (clay without breccia). If the slip surface occurs in tuff or tuffaceous materials and is subjected to increasing slide movement, the smectite content in the slip-surface clay increases, while the silicate mineral content decreases. Furthermore, the smectite content is observed to increase within the same landslide from the head to the toe portion of the landslide (direction of groundwater flow). The groundwater along the slip surface (above the impervious zone) contains an increased concentration of Ca⁺⁺ ions. As the concentration of HCO₃⁻ ions exceeds 40 mg/l, an environment is created that promotes the formation of smectite. This process indicates that there is an active ion exchange within the groundwater near the slip surface that forms smectite. Thus, the formation of smectite in the slip surface requires the presence of tuff and a sufficient concentration of HCO₃⁻ ions in the groundwater.

The study results presented here indicate that frictional resistance decreases as clay content increases. The reason for repeated movement of Japanese landslides in Tertiary tuffs or tuffaceous rocks at or in the immediate vicinity of the slip surface is attributed to: (1) an increase in clay materials along the slip surface as the slide movement is repeated and (2) the presence of groundwater that promotes the formation of smectite. As is commonly known, smectite is one of the clay minerals that has lowest frictional resistance.     

Building Damage and Casualties after an Earthquake

The relationship between building damage patterns and human casualties in Nishinomiya City – one of the most heavily damaged cities in the 1995 Hanshin-Awaji Earthquake Disaster – was investigated using photographs of damaged buildings. First, the photographs of buildings in which casualties occurred were identified, and the building damage patterns were judged based on the photographs considering the existence of survival space. Then the relationship between the building damage pattern and casualty occurrence, and the characteristics of casualty distribution, were investigated. The main findings were as follows: Most casualties occurred in relatively old two-story wooden buildings in which the ground floor completely collapsed without survival space; casualties occurred at all building damage levels including ``no damage', and it can be seen that building damage is the major, but not the sole cause, of casualties in an earthquake; in Nishinomiya City, the regional distributions of casualties due to the collapse of buildings that left no survival space is similar to that of casualties due to other types of building damage.     

Broad-band power-law spectra of well-log data in Japan

For the purpose of revealing the statistical characteristics of P -wave velocity, S -wave velocity and density in the uppermost part of the crust, we analysed well-log data obtained from five deep wells in different tectonic regions in Japan: three wells through the mainly sedimentary rocks in the Kanto plain and two wells in the Kuju volcano group in Kyushu Island. In the Kanto plain, the power spectral density of fractional fluctuation of P -wave velocity and that of density are proportional to a power of the spatial wavelength from a few metres to 100 m. where the power index (slope of the power spectral density at double logarithmic scale) is 1.1-1.3. At the Kuju volcano group, that of P - and S -wave velocity and density also obey a power law, with a power index of 1.3-1.6 for wavelengths from a few metres to few hundred metres. Correcting the effect of the moving box-car observation window which corresponds to the separation of two receivers of the logging tool, we find that the power-law characteristics hold for wavelengths down to a few tens of centimetres. The 1-D sections of the elastic inhomogeneities follow a kind of band-limited self-affine random process. Comparing the power spectral densities, we find smaller values of the power index in stable areas and larger values in tectonically active areas. The difference in the power index arises from long-wavelength components.