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     

Bending of spherical lithosphere–axisymmetric case

Effects of sphericity are commonly ignored in the lithospheric bending problem. In order to examine its effects, I solve a simple axisymmetric spherical-shell model. The full solution and the asymptotic solution are derived from the basic equations, and their relationship to the flat-plate solution is examined. For displacement, effects of sphericity are small, and use of the flat-plate solution produces results that are numerically indistinguishable from those of the spherical solution. The most significant effect of sphericity appears in the stress, in particular the normal stress along the strike direction of the trench. This stress is approximately given by Eu_r/R , where E is Young's modulus, u_r is the vertical deformation of the shell and R is its radius of curvature. If the shell (lithosphere) is bent downwards and reaches 30 km, this stress can become about 5 kbar in the Earth. While plastic behaviour may set in under such high pressure conditions and analysis beyond elasticity theory may be required, sphericity may be a cause of large compressive stress in the trench strike direction. This stress may play an important role in forming the overall shape of the Earth's subduction zones.     

Distribution and photo-physiological condition of phytoplankton in the tropical and subtropical North Pacific

To better understand the vertical distribution of phytoplankton in the tropical and subtropical North Pacific, we used fast repetition rate fluorometry to investigate the photo-physiological condition of the phytoplankton assemblage in this region between February and March 2007. Along 155°E, between the equator and 24°N, the peak of fluorescence (F _m), an indication of the deep chlorophyll maximum (DCM), was deeper than the top of the nitracline and occurred at the 2.4 ± 1.3 % (mean ± SD) light depth (relative to 0 m). The photochemical efficiency (F _v/F _m) and effective absorption cross-section of photosystem II (σ_PSII) were low at the surface but increased rapidly at depths between the top of the nitracline (40–138 m) and the DCM (70–158 m), an indication that the photo-physiological condition of the phytoplankton improved below the top of the nitracline. The depth of the maximal F _v/F _m [Z(F _v/F _{m max})] was 18–32 m deeper than the DCM and corresponded to the 0.8 ± 0.2 % light depth. The values of F _v/F _m at the Z(F _v/F _{m max}) were 20 % higher than those at the DCM and averaged 0.48 ± 0.01. These results suggest that the phytoplankton assemblage beneath the DCM had a high potential photosynthetic performance capacity and was growing by using the very low ambient light in this region.     

Formalism for traveltime inversion with finite frequency effects

A simple modification of the waveform inversion formula, based on the normal mode perturbation theory, is shown to lead to a formula for traveltime anomalies. The kernel which is derived can be used for traveltime inversion with automatic inclusion of finite frequency effects. Inversion for Earth structure with such kernels will lead to better resolution estimates than ray-theoretical traveltime inversion. Examples of kernels for transverse component seismograms are shown for direct S waves, ScS , Love waves and diffracted S waves. A measure of finite frequency effects is also proposed by comparing our formula with the one from ray theory. A quantity which should be 1 in the case of ray theory is computed for the finite frequency kernels and is shown to have deviations up to about 30 per cent from 1. Therefore, the use of ray theory for long-period body waves applies incorrect weight along a ray path and may introduce a small bias to an earth model.     

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.     

Magnetic properties of the Fe2SiO4-Fe3O4 spinel solid solutions

 Magnetic measurement of Fe_{3− x} Si _x O₄ spinel solid solutions indicates that their Curie temperatures decrease gradually, but not linearly, from 851 to 12 K with increasing content of nonmagnetic ions Si⁴⁺. Magnetic hysteresis becomes more noticeable in solid solutions having a larger content of Fe₂SiO₄. Saturation magnetizations of Fe_{3− x} Si _x O₄ samples increase up to x=0.357 and they are easily saturated in the field of H=0.1 T. However, magnetization of the sample of x=0.794 does not approach saturation even at high field of H=7.0 T and has a large coercive force. The Si⁴⁺ disordered distribution is confirmed to be ^tetr[Fe³⁺ _{1− x + x t} Si⁴⁺ _{x (1− t )}] ^octa[Fe²⁺ _{1+ x} Fe³⁺ _{1− x − x t} Si⁴⁺ _{x t} ] O₄ by the spin moment, which is consistent with site occupancy obtained from X-ray crystal structure refinement. Their molecular magnetizations would be expressed as M _B={4(1+x)+10xt}μ_B as functions of composition parameter x and Si⁴⁺ ordering parameter t of the solid solution. The sample of x=0.794 is antiferromagnetic below the Néel temperature, mainly due to the octahedral cation interaction M _O–M _O, while both M _T–M _O and M _O–M _O interactions induce a ferrimagnetic property. Concerning magnetic spin configuration, in the case of x>0.42, the lowest dɛ level becomes a singlet, resulting in no orbital angular momentum. Received: 20 April 2000 / Accepted: 11 September 2000     

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.     

Clinopyroxene-perovskite phase transition of FeGeO3 under high pressure and room temperature

In order to confirm the possible existence of FeGeO₃ perovskite, we have performed in situ X-ray diffraction measurements of FeGeO₃ clinopyroxene at pressures up to 40 GPa at room temperature. The transition of FeGeO₃ clinopyroxene into orthorhombic perovskite is observed at about 33GPa. The cell parameters of FeGeO₃ perovskite are a=4.93(2) Å, b=5.06(6) Å, c=6.66(3) Å and V=166(3) ų at 40 GPa. On release of pressure, the perovskite phase transformed into lithium niobate structure. The previously reported decomposition process of clino-pyroxene into Fe₂GeO₄ (spinel)+GeO₂ (rutile) or FeO (wüstite) +GeO₂ (rutile) was not observed. This shows that the transition of pyroxene to perovskite is kinetically accessible compared to the decomposition processes under low-temperature pressurization.