Equation of state of iron–silicon alloys to megabar pressure

The stability and pressure–volume equation of state of iron–silicon alloys, Fe-8.7 wt% Si and Fe-17.8 wt% Si, have been investigated using diamond-anvil cell techniques up to 196 and 124 GPa, respectively. Angular–dispersive X-ray diffractions of iron–silicon alloys were measured at room temperature using monochromatic synchrotron radiation and an imaging plate (IP). A bcc–Fe-8.7 wt% Si transformed to hcp structure at around 1636 GPa. The high-pressure phase of Fe-8.7 wt% Si with hexagonal close-packed (hcp) structure was found to be stable up to 196 GPa and no phase transition of bcc–Fe-17.8 wt% Si was observed up to 124 GPa. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state (BM EOS) with zero–pressure parameters: V₀=22.2(8) ų, K₀=198(9) GPa, and K₀=4.7(3) for hcp–Fe-8.7 wt% Si and V₀=179.41(45) ų, K₀=207(15) GPa and K₀=5.1(6) for Fe-17.8 wt% Si. The density and bulk sound velocity of hcp–Fe-8.7 wt% Si indicate that the inner core could contain 3–5 wt% Si.     

Element partitioning between metallic liquid, silicate liquid, and lower-mantle minerals: implications for core formation of the Earth

We determined the partition coefficients of 19 elements between metallic liquid and silicate liquid at 20 GPa and 2500°C, and between metallic liquid and silicate perovskite at 27 GPa and 2200°C. Remarkable differences were observed in the partitioning behaviors of Si, P, W, Re, and Pb among the silicate liquid, perovskite, and magnesiowüstite coexisting with metallic liquid, reflecting incompatibility of the elements in the silicate or oxide phase. We could not observe any significant difference in the partitioning behaviors of V, Cr, Mn, Co, Ni, and Cu among the phases coexisting with metallic liquid.

Comparison of the present partitioning data with those obtained previously at lower pressure and temperature suggests that the exchange partition coefficients, K_met/sil, of Co, Ni, Mo, and W decrease, whereas those of V, Cr, and Mn increase and tend to approach unity with increasing pressure and temperature. We also made preliminary experiments to clarify the effect of sulfur on the partitioning behaviors. Sulfur lowers the exchange partition coefficients, K_met/sil, of Mo and W between metallic liquid and silicate liquid significantly at 20 GPa and 2300°C.

The mantle abundances of Co, Ni, Cu, Mo, and W calculated for the metal-silicate equilibrium model are lower than those of the real mantle, whereas P, K, and Mn are overabundant in the calculated mantle. The discrepancies in the abundances of Co and Ni could be explained by the chemical equilibrium at higher pressure and temperature. Large discrepancies in Mo and W between the calculated and real mantles could be accounted for by the effect of sulfur combined with the effects of pressure and temperature on the chemical equilibrium. The mantle abundances of P, K, and Cu could be accounted for by volatile loss in the nebula, perhaps before accretion of the Earth, combined with the chemical equilibrium at higher pressure and temperature. Thus the observed mantle abundances of P, K, Co, Ni, Cu, Mo, and W may be consistent with a model of sulfur-bearing metal-silicate equilibrium in lower-mantle conditions.     

Partitioning of elements between majorite garnet and melt and implications for petrogenesis of komatiite

Partitioning of elements between majorite garnet and ultrabasic melt has been studied at 16 GPa and 1950° C. Ca, Ti, La, Sm, Gd, Zr, Hf, Fe, Ni, Mn, K, and Na are enriched in the melt, whereas Al, Cr, V, Sc and Yb are concentrated in majorite garnet. Thus, majorite garnet fractionation by partial melting could produce chemical heterogeneities in these elements deviating from chondritic abundance. Using the partitioning behaviour of elements between majorite garnet and ultrabasic melt, the petrogenesis of komatiite is discussed. A simple model to explain the chemical varieties of komatiites is as follows. Aluminadepleted komatiite was generated by partial melting of the primitive mantle at 200–650 km depth, and alumina-enriched komatiite is the product of remelting of the residual solid at the same depths, whereas alumina-undepleted komatiite was formed by partial melting of the primitive upper mantle at depths shallower than 200 km. We suggest the possibility of large-scale chemical layering or heterogeneity in the early Archean upper mantle as an alternative model for komatiite genesis; shallower mantle depleted in majorite garnet and the underlying mantle enriched in majorite garnet. Alumina-depleted and alumina-enriched komatiites in the early Archean might be generated by a high degree of partial melting of the layered mantle. Such chemical layering could have been homogenized by the late Archean. This explains the observations that alumina-depleted and alumina-enriched komatiites were generally formed in the early Archean but alumina-undepleted komatiite was erupted in the late Archean.     

Borehole water and hydrologic model around the Nojima fault, SW Japan

The active fault drilling at Nojima Hirabayashi after the 1995 Hyogoken-nanbu (Kobe) earthquake (M_JMA = 7.2) provides us with a unique opportunity to investigate subsurface fault structure and the in-situ properties of fault and fluid. The borehole intersected the fault gouge of the Nojima fault at a depth interval of 623 m to 625 m. The lithology is mostly Cretaceous granodiorite with some porphyry dikes.The fault core is highly permeable due to fracturing. The borehole water was sampled in 1996 and 2000 from the depth interval between 630 and 650 m, just below the fault core. The chemical and isotopic compositions were analyzed. Carbon and oxygen isotope ratios of carbonates from the fault core were analyzed to estimate the origin of fluid.The following conclusions were obtained. (1) The ionic and isotopic compositions of borehole water did not change from 1996 to 2000. They are mostly derived from local ground water as mentioned by Sato and Takahashi [Sato, T., Takahashi, M., 2000. Chemical and isotopic compositions of groundwater obtained from the Hirabayashi well. Geological Survey of Japan Interim Report No. EQ/00/1, 187–192.]. (2) Geochemical speciation revealed that the borehole water was derived from a relatively deep reservoir, which may be situated at a depth of 3 to 4 km where the temperature is about 80–90 °C. (3) The shallower part of the Nojima fault (shallower than the reservoir depth) has not been healed from the hydrological viewpoints 5 years after the event, in contrast to the rapid healing detected by S wave splitting [Tadokoro, K., Ando, M., 2002. Evidence for rapid fault healing derived from temporal changes in S wave splitting, Geophys. Res. Lett., 29, 10.1029/2001GL013644.]. (4) Precipitation of calcite from the present borehole water since drilling supports the idea of precipitation of some calcite in coseismic hydraulic fractures in the fault core [Boullier, A-M., Fujimoto, K., Ohtani, T., Roman-Ross, G., Lewin, E., Ito, H., Pezard, P., Ildefonse, B., 2004. Textural evidence for recent co-seismic circulation of fluids in the Nojima fault zone, Awaji Island, Japan., Tectonophysics, 378, 165–181.]. (5) Carbon and oxygen isotope ratios of calcite indicated that the meteoric water flux had been localized at the fault core. (6) A difference in the carbon isotope ratio between the footwall and the hanging wall suggests that the fault has been acted as a hydrologic barrier, although the permeability along the fault is still high.     

Discovery of Jurassic ammonoids from the Shyok suture zone to the northeast of Chang La Pass, Ladakh, northwest India and its tectonic significance

Abstract   Callovian (late Middle Jurassic) ammonoids Macrocephalites and Jeanneticeras were recovered from the Shyok suture zone, northeast of Chang La Pass, Ladakh, northwest India. They are the first reliable Jurassic fossils and the oldest chronologic data from the Shyok suture zone. The ammonoid-bearing Jurassic strata, newly defined as the Tsoltak Formation, consist largely of terrigenous mudstone with thin sandstone beds and were probably a part of the continental basement to the Cretaceous Ladakh Arc.     

A practical model to estimate photosynthetically active radiation using general meteorological elements in a temperate humid area and comparison among models

Although accurately evaluating photosynthetically active radiation is important, much effort is required to measure this radiation using a quantum sensor. We develop a new model that makes estimates using only general meteorological data—solar radiation, atmospheric pressure, air temperature, and relative humidity. Root mean square deviations for eight datasets at five sites in Japan were smaller than 5.2 %, similar to error in other studies and to individual differences of quantum sensors. Most root mean square deviations of nine previous models and our eight datasets are larger than that of the new estimation model, which performed well. This suggests that the model is useful for estimating photosynthetically active radiation in a temperate, humid area of Japan.     

Effect of hydrogen on the melting temperature of FeS at high pressure: Implications for the core of Ganymede

We have carried out in situ X-ray diffraction experiments on the FeS–H system up to 16.5 GPa and 1723 K using a Kawai-type multianvil high-pressure apparatus employing synchrotron X-ray radiation. Hydrogen was supplied to FeS from the thermal decomposition of LiAlH₄, and FeSH_x was formed at high pressures and temperatures. The melting temperature and phase relationships of FeSH_x were determined based on in situ powder X-ray diffraction data. The melting temperature of FeSH_x was reduced by 150–250 K comparing with that of pure FeS. The hydrogen concentration in FeSH_x was determined to be x = 0.2–0.4 just before melting occurred between 3.0 and 16.5 GPa. It is considered that sulfur is the major light element in the core of Ganymede, one of the Galilean satellites of Jupiter. Although the interior of Ganymede is differentiated today, the silicate rock and the iron alloy mixed with H₂O, and the iron alloy could react with H₂O (as ice or water) or the hydrous silicate before the differentiation occurred in an early period, resulting in a formation of iron hydride. Therefore, Ganymede's core may be composed of an Fe–S–H system. According to our results, hydrogen dissolved in Ganymede's core lowers the melting temperature of the core composition, and so today, the core could have solid FeSH_x inner core and liquid FeH_x–FeSH_x outer core and the present core temperature is considered to be relatively low.     

The compressibility of Fe- and Al-bearing phase D to 30 GPa

High-pressure in situ X-ray diffraction experiment of Fe- and Al-bearing phase D (Mg_0.89Fe_0.14Al_0.25Si_1.56H_2.93O₆) has been carried out to 30.5 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields values of V ₀ = 86.10 ± 0.05 ų; K ₀ = 136.5 ± 3.3 GPa and K′ = 6.32 ± 0.30. If K′ is fixed at 4.0 K ₀ = 157.0 ± 0.7 GPa, which is 6% smaller than Fe–Al free phase D reported previously. Analysis of axial compressibilities reveals that the c-axis is almost twice as compressible (K _c  = 93.6 ± 1.1 GPa) as the a-axis (K _a  = 173.8 ± 2.2 GPa). Above 25 GPa the c/a ratio becomes pressure independent. No compressibility anomalies related to the structural transitions of H-atoms were observed in the pressure range to 30 GPa. The density reduction of hydrated subducting slab would be significant if the modal amount of phase D exceeds 10%.     

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle,and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

We performed an experimental study, designed to reproduce the formation of an unusual merwinite?+?olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca?=?1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite?+?olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300–1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca#?=?molar 100?×?Ca/(Ca?+?Mg)?>?0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca?=?1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg₂SiO₄ (olivine)?+?6CaCO₃ (liquid)?=?Ca₃MgSi₂O₈ (merwinite)?+?3CaMg(CO₃)₂ (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.     

Study of pocyclic aromatic hydrocarbons at a pressure of 6–9 GPa with X-ray diffraction and synchrotron radiation

This work is one of the stages of study of the deep C-O-H fluid and investigates the behavior of polycyclic aromatic hydrocarbons (PAHs) under conditions of the Earth’s mantle. The composition of the C-O-H fluid in the upper mantle is estimated as a mixture of H₂O and CH₄ with a minor amount of H₂ and heavier hydrocarbons. Some theoretical calculations show that the stability of heavy hydrocarbons (alkanes, alkenes, and PAHs) increases with an increase in temperature. This paper presents the results of an XRD study of PAHs stability in multianvil presses on a Spring-8 accelerator (Japan). The primary compositions were chosen according to the abundance of PAHs in nature. In situ diffraction spectrums were recorded to determine the PAHs stability field. It was established that the PAHs become unstable at a pressure of 6–9 GPa and a temperature of 873–1073 K.