A Method to Suppress Isobaric and Polyatomic Interferences for Measurements of Highly Siderophile Elements in Desilicified Geological Samples

Sample decomposition using inverse aqua regia at elevated temperatures and pressures (e.g., Carius tube or high‐pressure asher) is the most common method used to extract highly siderophile elements (HSEs: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) from geological samples. Recently, it has been recognised that additional HF desilicification is necessary to better recover HSEs, potentially contained within silicate or oxide minerals in mafic samples, which cannot be dissolved solely by inverse aqua regia. However, the abundance of interfering elements tends to increase in the eluent when conventional ion‐exchange purification procedures are applied to desilicified samples. In this study, we developed an improved purification method to determine HSEs in desilicified samples. This method enables the reduction of the ratios of isobaric and polyatomic interferences, relative to the measured intensities of HSE isotope masses, to less than a few hundred parts per million. Furthermore, the total procedural blanks are either comparable to or lower than conventional methods. Thus, this method allows accurate and precise HSE measurements in mafic and ultramafic geological samples, without the need for interference corrections. Moreover, the problem of increased interfering elements, such as Zr for Pd and Cr for Ru, is circumvented for the desilicified samples.     

Predictive modelling of rainfall-induced landslide hazard in the Lesser Himalaya of Nepal based on weights-of-evidence

Landslide hazard mapping is a fundamental tool for disaster management activities in mountainous terrains. The main purpose of this study is to evaluate the predictive power of weights-of-evidence modelling in landslide hazard assessment in the Lesser Himalaya of Nepal. The modelling was performed within a geographical information system (GIS), to derive a landslide hazard map of the south-western marginal hills of the Kathmandu Valley. Thematic maps representing various factors (e.g., slope, aspect, relief, flow accumulation, distance to drainage, soil depth, engineering soil type, landuse, geology, distance to road and extreme one-day rainfall) that are related to landslide activity were generated, using field data and GIS techniques, at a scale of 1:10,000. Landslide events of the 1970s, 1980s, and 1990s were used to assess the Bayesian probability of landslides in each cell unit with respect to the causative factors. To assess the accuracy of the resulting landslide hazard map, it was correlated with a map of landslides triggered by the 2002 extreme rainfall events. The accuracy of the map was evaluated by various techniques, including the area under the curve, success rate and prediction rate. The resulting landslide hazard value calculated from the old landslide data showed a prediction accuracy of > 80%. The analysis suggests that geomorphological and human-related factors play significant roles in determining the probability value, while geological factors play only minor roles. Finally, after the rectification of the landslide hazard values of the new landslides using those of the old landslides, a landslide hazard map with > 88% prediction accuracy was prepared. The methodology appears to have extensive applicability to the Lesser Himalaya of Nepal, with the limitation that the model's performance is contingent on the availability of data from past landslides.     

Molecular dynamics study of pressure-induced transformation of quartz-type GeO2

We simulated quartz-type GeO₂ and investigated its high-pressure transformation using the molecular dynamics (MD) simulation method with a model potential. The calculated results under hydrostatic compression indicated that a pressure-induced amorphization of quartz-type GeO₂ originated from the mechanical instability of the quartz lattice as, in previous theoretical studies of SiO₂. Furthermore, quartz-type GeO₂ directly transformed to a rutile-like structure with only subtle displacements of ions under σ _{x y} imposed shear stressed decompression. This is the first reproduction of the quartz-to-rutile transformation. A possible pathway of this transition is proposed in this study. Received: 14 April 1999 / Revised, accepted: 11 August 1999     

Low-frequency variations of the Eastern Subtropical Front in the North Pacific in an eddy-resolving ocean general circulation model: roles of central mode water in the formation and maintenance

Temporal variations (1960–2005) of the Eastern Subtropical Front (ESTF) in the North Pacific are investigated using historical-run output data of the eddy-resolving Meteorological Research Institute Community Ocean Model, forced by atmospheric reanalysis dataset. Simulated ESTF is distributed in a region of zonal band of 24°N–30°N east of the International Date Line, and is located at the southern boundary of the central mode water (CMW) north of the front. The ESTF intensity clearly shows an interdecadal variation with a timescale of about 20?years. This variation is associated with that in the potential vorticity of CMW, which originates in the CMW formation region farther north about 3?years earlier due to changes in the surface wind forcing.     

Molecular orbital study on the onset of the pressure-induced transformations of the metastably compressed germanates

In order to elucidate the onset of the pressure-induced transformations of germanates consisting of GeO₄ tetrahedra at room temperature, we have investigated the stability of the crystal structures near the transition pressure in terms of the stability of the linkage of the tetrahedra. The stability of the linkage near the transition pressure is estimated from the results of the molecular orbital calculations for the model cluster H₆Ge₂O₇, which mimics the linkage of tetrahedra, as functions of the bond length d(Ge–O_br) with bridging oxygen and bond angles Ge–O_br–Ge. The calculation shows that the total energy of the linkage becomes minimum at d(Ge–O_br)=1.758 Å and br–Ge=130.4°, and that it increases with the deviation from the energy minimum geometry. From the compression behavior of framework and chain germanates, we find that the linkage of the tetrahedra becomes unstable with increasing pressure, and that these germanates commonly transform into their high-pressure phases when the linkage of the tetrahedra largely departs from the energy minimum geometry. This suggests that the high-pressure transformations of the metastably compressed germanates are induced by the instability of the linkage of tetrahedra.     

Carbon isotopic thermometry and geobarometry of sillimanite isograd in thermal aureoles: the depth of emplacement of upper crustal granitic bodies

Carbon isotope fractionation between coexisting calcite and graphite (C ) has been studied in metamorphosed limestones from three thermal aureoles around Cretaceous granitic bodies (i.e., Tanohata, Tono, and Senmaya aureoles) in the Kitakami Mountains, Northeast Japan. C in each aureole decreases toward the granitic bodies, and becomes virtually uniform near the sillimanite isograd for metapelites, although calcite has variable isotopic ratios reflecting the original sedimentary compositions. The relationships indicate that isotopic equilibrium has been attained in metamorphosed limestone of sillimanite grade. Estimated C at the sillimanite isograd is similar in the Tanohata and Tono aureoles, but different in the Senmaya aureole with smaller carbon isotopic fractionations. From the temperature dependence of C and the negative dP/dT of andalusite–sillimanite equilibrium, we conclude that the sillimanite isograd in the Senmaya aureole was under higher temperature and lower pressure than in the other two localities. Temperatures at the sillimanite isograd are estimated by using existing calibrations of carbon isotopic exchange between calcite and graphite, whereas pressures are estimated from carbon isotopic temperatures and the andalusite–sillimanite equilibrium (Holdaway and Mukhopadhyay 1993a). Consistency of the P–T estimates is examined in the light of phase equilibria in the pelitic system. The estimated pressures at the sillimanite isograd are at about 2.1–2.7(±0.2) kbar for the Tanohata and Tono aureoles and less than 1 kbar for the Senmaya aureole, respectively. Geobarometry of sillimanite isograd in thermal aureoles indicates a marked difference in the depth of solidification of upper crustal granitoids: the Senmaya pluton has intruded and solidified at a very shallow level of less than 4 km whereas the Tanohata and Tono plutons are more deep-seated (ca. 8–10 km). The method can also be an effective tool in studying low-pressure type metamorphism in which geothermobarometry using garnet is not always applicable.Editorial responsibility: J. Hoefs     

Carbon isotopic study on coexisting calcite and graphite in the Ryoke metamorphic rocks,northern Kiso district,central Japan

Carbon isotope fractionation between coexisting calcite and grpahite ( ¹³C_cc-gr) has been determined in metamorphosed limestones and calc-silicate rocks from the Ryoke metamorphic belt in the northern Kiso district. In this district, the Ryoke metamorphic rocks, ranging from the lower greenschist facies to the upper amphibolite facies, are widely distributed. The fractionation of ¹³C/¹²C between calcite and graphite decreases regularly with increasing metamorphic grade and is independent of absolute ¹³C values of calcite. This evidence suggests that carbon isotopic exchange equilibrium has been attained during metamorphism even in the greenschist facies and isotopic modification, possibly caused by retrogressive metamorphism, is not distinguished. For T=270–650° C, the fractionation is expressed by the following equation: ¹³C_cc-gr=8.9×10⁶T^–2–7.1 (T in °K).This equation has a slope steeper than the current results on the ¹³C_cc-gr versus 10⁶T^–2 diagram. It can be used as a potential geothermometer for almost the entire temperature range of metamorphism. ¹³C values of carbonaceous matter in unmetamorphosed limestones in this district are approximately –22, due to its biogenic origin. Graphite from metamorphosed limestones is also considered to be of biogenic origin but shows enrichment of ¹³C due to isotopic exchange with calcite. ¹³C values of graphite as well as ¹³C_cc-gr confirm that zone II represents the lowest grade zone of Ryoke metamorphism. The maximum equilibrium fractionation of ¹³C between calcite and graphite is considered to be approximately 23%, which corresponds to 270° C. Below this temperature, it seems that carbon isotopic exchange between the minerals does not occur.Calcite in marble from the higher grade zones has relatively lower ¹³C and ¹⁸O values. The depletion of heavy isotopes is considered to be caused by the loss of ¹³C and ¹⁸O enriched carbon dioxide during decarbonation reactions. For oxygen, it is considered that isotopic exchange with metamorphic fluids plays an important role in lowering the ¹⁸O value of calcite in some higher grade marbles.     

Crystal structures of Ni2SiO4 and Fe2SiO4 as a function of temperature and heating duration

X-ray structure refinements of Ni₂SiO₄ and Fe₂SiO₄ spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni₂SiO₄ spinel linearly increased with temperature up to 1,000° C. However, Fe₂SiO₄ spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D _oct/D _tetr and between the shared and unshared edge distances (O-O)_sh/(O-O)_unsh in Fe₂SiO₄ spinel were both much larger than those in Ni₂SiO₄. These ratios increase with temperature. The Fe₂SiO₄ spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni₂SiO₄ spinel. The lattice parameter of Ni₂SiO₄ spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.