An atomic level study of rhenium and radiogenic osmium in molybdenite

Local atomic structures of Re and radiogenic Os in molybdenite from the Onganja mine, Namibia, were examined using X-ray absorption fine structure (XAFS). Rhenium L_III-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) show that the oxidation state of Re, the interatomic distances between Re and the neighboring atoms, and the coordination number of Re to S are very similar to those of Mo in molybdenite. The results confirm that Re is present as Re(IV) in the Mo site in molybdenite.Measurement of L_III-edge XANES and EXAFS of a minor concentration (8.55 ppm) of radiogenic Os was accomplished in fluorescence mode by removing the interfering X-rays from Re and other elements using a crystal analyzer system. The data indicate that the oxidation state of radiogenic Os is Os(III) and Os(IV) and clearly different from Os(II) in natural sulfide minerals, such as OsS₂ (erlichmanite). XANES data also suggest that radiogenic Os does not form a secondary Os phase, such as OsS₂ or Os metal, in molybdenite.EXAFS of radiogenic Os was successfully simulated assuming that Os is present in the Mo site in molybdenite. The data are consistent with the XANES data; Os does not form Os phases in molybdenite. The EXAFS simulation showed that the interatomic distance between Os and S is 2.27 Å, which is 0.12 Å smaller than the distances of Re-S and Mo-S (2.39 Å) in molybdenite. Similar valences and ionic sizes of Re and Mo in molybdenite support the fact that large amounts of Re can be incorporated into the Mo site as has been observed in previous studies, whereas the different properties of Os compared to Mo and Re suggested here support much lower abundance of common Os in molybdenite. This makes molybdenite an ideal mineral for the Re-Os geochronometer as shown in many studies. However, the shorter distance between radiogenic Os and S compared to those of Re-S and Mo-S in molybdenite suggests that the radiogenic Os has a smaller ionic size than Re(IV) and Mo(IV). Furthermore, Os may be partly present as Os(III). Smaller and lower charge Os can diffuse faster than larger and higher charge Re in molybdenite at a given set of conditions. Hence, our study provides an atomic-level explanation for the high mobility of Os compared to Re, which has been suggested by earlier workers using laser ablation ICP-MS.     

Oscillatory behavior of monsoon rainfall over Sri Lanka during the late 19th and 20th centuries and its relationships to SSTs in the Indian Ocean and ENSO

Summary In this study, we have analyzed the temporal oscillations of precipitation in meso-scale zones of Sri Lanka to examine potential existence of periodic oscillatory behavior in rainfall. Only a few statistically significant cycles were identified: a 3.5-year cycle in most of central Sri Lanka during the January–March rainfall regime and a cycle of the same length in southwestern Sri Lanka during the October regime. A 2.1-year cycle marks the northeastern parts of Sri Lanka during the December/April contrast rainfall regime. This cycle is shown to be strongly related to Quasi-Biennial Oscillation. October and November rainfall are found to be coupled with ENSO fluctuations, and on average, more than 900 mm more rainfall is observed per month over all stations during El Ni?o than during La Ni?a years. Analysis of relationships between the observed meso-scale rainfall regions and the Sea Surface Temperatures (SSTs) in the Indian Ocean north of the Equator showed that the northern Indian Ocean can be divided into three particular regions based on similarity in the SST fluctuations: (a) a region with cool upwelling water, (b) non upwelling water, and (c) the Indian Ocean Warm Pool. We found that there are no statistically significant relationships between the observed SST regions in the Indian Ocean and the meso-scale precipitation patterns in Sri Lanka.     

Distribution of trace elements in subcellular fractions of three aquatic birds

This study investigated the subcellular distribution of Cu, Zn, Cd and Ag in liver of mallard (Anas platyrhynchos), spot-billed duck (A. poecilorhyncha) and great cormorant (Phalacrocorax carbo) to better understand metal fractionation and dynamics in avian liver. Most of the total Cu, Zn, Cd and Ag were present in hepatocytosol, and their concentrations increased with total hepatic levels in all the three avian species. Copper, Zn and Cd in hepatocytosol were present mostly in metallothionein fractions (MTs), and Cu and Cd contents in this fraction were positively correlated with hepatocytosol levels in all the species. Silver was observed mostly in both high-molecular weight and MT fractions in hepatocytosol in mallard and great cormorant, whereas it was present in both low-molecular weight and MT fractions in spot-billed duck, suggesting that distribution of Ag in the hepatocytosol was species-specific. The elution profile of metals in MT fractions revealed six metallic peaks in mallard and spot-billed duck, and three peaks in great cormorant, implying the presence of multiple MT isoforms in the liver of these avian species. The present study demonstrated that MTs are closely associated with metal regulation, especially Cu and Cd, in these three aquatic birds.     

High-temperature and high-pressure equation of state for the hexagonal phase in the system NaAlSiO4 – MgAl2O4

Thermal equation of state of an Al-rich phase with Na_1.13Mg_1.51Al_4.47Si_1.62O₁₂ composition has been derived from in situ X-ray diffraction experiments using synchrotron radiation and a multianvil apparatus at pressures up to 24 GPa and temperatures up to 1,900 K. The Al-rich phase exhibited a hexagonal symmetry throughout the present pressure–temperature conditions and the refined unit-cell parameters at ambient condition were: a=8.729(1) Å, c=2.7695(5) Å, V ₀=182.77(6) Å³ (Z=1; formula weight=420.78 g/mol), yielding the zero-pressure density ρ₀=3.823(1) g/cm³ . A least-square fitting of the pressure-volume-temperature data based on Anderson’s pressure scale of gold (Anderson et al. in J Appl Phys 65:1534–543, 1989) to high-temperature Birch-Murnaghan equation of state yielded the isothermal bulk modulus K ₀=176(2) GPa, its pressure derivative K ₀ ^′ =4.9(3), temperature derivative (?K _T /?T) _P =?0.030(3) GPa K^?1 and thermal expansivity α(T)=3.36(6)×10^?5+7.2(1.9)×10^?9 T, while those values of K ₀=181.7(4) GPa, (?K _T /?T) _P =?0.020(2) GPa K^?1 and α(T)=3.28(7)×10^?5+3.0(9)×10^?9 T were obtained when K ₀ ^′ was assumed to be 4.0. The estimated bulk density of subducting MORB becomes denser with increasing depth as compared with earlier estimates (Ono et al. in Phys Chem Miner 29:527–531 2002; Vanpeteghem et al. in Phys Earth Planet Inter 138:223–230 2003; Guignot and Andrault in Phys Earth Planet Inter 143–44:107–128 2004), although the difference is insignificant (<0.6%) when the proportions of the hexagonal phase in the MORB compositions (～20%) are taken into account.     

Critical damping of structures with elastically supported visco‐elastic dampers

This paper presents a new formulation for critical damping of structures with elastically supported visco‐elastic dampers.Owing to the great dependence of damper performance on the support stiffness, this model is inevitable for reliable modelling of structures with visco‐elastic dampers. It is shown that the governing equation of free vibration of this model is reduced to a third‐order differential equation and the conventional method for defining the critical damping for second‐order differential equations cannot be applied to the present model. It is demonstrated that the region of overdamped vibration is finite in contrast to that (semi‐infinite) for second‐order differential equations and multiple critical damping coefficients exist. However, it turns out that the smaller one is practically meaningful. Copyright © 2001 John Wiley & Sons, Ltd.     

In situ X-ray observations of phase transitions in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel to 40 GPa using multianvil apparatus with sintered diamond anvils

 Phase transitions in MgAl₂O₄ spinel have been studied at pressures 22–38 GPa, and at temperatures up to 1600 °C, using a combination of synchrotron radiation and a multianvil apparatus with sintered diamond anvils. Spinel dissociated into a mixture of MgO plus Al₂O₃ at pressures to 25 GPa, while it transformed to the CaFe₂O₄ (calcium ferrite) structure at higher pressures via the metastably formed oxide mixture upon increasing temperature. Neither the e-phase nor the CaTi₂O₄-type MgAl₂O₄, which were reported in earlier studies using the diamond-anvil cell, were observed in the present pressure and temperature range. The zero-pressure bulk modulus of the calcium-ferrite-type MgAl₂O₄ was calculated as K=213 (3) GPa, which is significantly lower than that reported by Yutani et al. (1997), but is consistent with a more recent result by Funamori et al. (1998) and that estimated by an ab initio calculation by Catti (2001). Received: 2 April 2002 / Accepted: 29 July 2002 Acknowledgements The authors thank Y. Higo, Y. Sueda, T.␣Ueda, Y. Tanimoto, A. Fukuyama, K. Ochi, F. Kurio and T. Kawahara for help in the in situ X-ray observations at SPring-8 (No: 2000A0061-CD-np and 2000B0093-ND-np). We also thank W.␣Utsumi, J. Ando and O. Shimomura for advice and encouragement during this study, and N. Funamori and an anonymous reviwer for comments on the article. The present study is partly supported by the grant-in-aid for Scientific Research (A) of the Ministry of Education, Science, Sport and Culture of the Japanese government (no: 11694088).     

Raman spectra of hydrous γ -Mg2SiO4 at various pressures and temperatures

 One well-defined OH Raman band at 3651 ± 1 cm⁻¹ and one weak feature near 3700 ± 5 cm⁻¹ are recognized for the hydrous γ-phase of Mg₂SiO₄. Like the hydrous β-phase, the H₂O content in the γ-phase shifts most of the corresponding silicate modes towards lower frequencies. Variations in Raman spectra of the hydrous γ-phase were investigated up to about 200 kbar at room temperature and in the range 81–873 K at atmospheric pressure. Unlike the anhydrous γ-phase, which remains intact up to at least 873 K, the hydrous γ-phase sometimes converts to a defective forsterite structure above 800 K. Although the hydrous γ-phase remains intact up to at least 800 K, Raman signals of the OH bands disappear completely above 423 K. The Raman frequency of the well-defined OH band decreases linearly with increasing temperature between 81 and 423 K. In the region of the silicate vibrations, the Raman frequencies of the two most intense bands increase nonlinearly with increasing pressure, and decrease with increasing temperature. The frequencies for all other weak bands, however, decreased linearly with increasing temperature. The latter most likely reflects the larger scatter of the data for the weak bands. Received: 27 April 2001 / Accepted: 12 September 2001     

Seismic return motion

Possibilities of backswing of fault displacement are investigated on the basis of a simple crack model. Although it has been suggested that the backswing would not occur in real earthquakes because of friction, there is evidence that some earthquakes might have caused return motion “locally” on the fault surface. This paper attempts to derive conditions for such local return motion. Spatial extension of the crack beyond the stress-filled region into the stress-deficient region gives a favorable site for the return motion, the site being just outside the stress-filled region. In our model the return motion occurs at this site when the frictional stress is less than about 30% of the regional stress in the stress-filled region. The overall return motion, on the other hand, would not occur unless the frictional stress is less than 10% of the regional stress.     

Sulphide and oxide minerals from the Ohmine granitic rocks in Kii Peninsula,central Japan,and their primary paragenetic relations

In the Ohmine granitic rocks of Kii Peninsula, central Japan, ilmenite, rutile, pyrrhotite, pyrite and chalcopyrite commonly occur, but no magnetite is present. Their primary paragenetic relations were confirmed by examining their mode of occurrences as inclusion species in major silicate minerals and the phase relations in the Cu-Fe-S system, though their parageneses changed in cooling of the rocks. This makes it possible to estimate the fugacities of oxygen and sulfur in the granitic rocks based upon their paragenetic relations, and to discuss the nature of volatiles in the granitic rocks. Significant subsolidus reactions for sulfide minerals continued until the rocks cooled below 300° C and took place in two types of mineral grains, in groundmass and as inclusions. The removal of sulfur and copper through the silicate crystals was too easy to preserve the chemistry of sulfides included in silicates.