Takaya Nagai

Hokkaido University, Sapporo, Hokkaidō, Japan

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Publications (45)119.12 Total impact

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    Jun Kawano · Hiroshi Sakuma · Takaya Nagai
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    ABSTRACT: First-principles calculations of Mg2+-containing aragonite surfaces are important because Mg2+ can affect the growth of calcium carbonate polymorphs. New calculations that incorporate Mg2+ substitution for Ca2+ in the aragonite {001} and {110} surfaces clarify the stability of Mg2+ near the aragonite surface and the structure of the Mg2+-containing aragonite surface. The results suggest that the Mg2+ substitution energy for Ca2+ at surface sites is lower than that in the bulk structure and that Mg2+ can be easily incorporated into the surface sites; however, when Mg2+ is substituted for Ca2+ in sites deeper than the second Ca2+ layer, the substitution energy approaches the value of the bulk structure. Furthermore, Mg2+ at the aragonite surface has a significant effect on the surface structure. In particular, CO3 groups rotate to achieve six-coordinate geometry when Mg2+ is substituted for Ca2+ in the top layer of the {001} surface or even in the deeper layers of the {110} surface. The rotation may relax the atomic structure around Mg2+ and reduces the substitution energy. The structural rearrangements observed in this study of the aragonite surface induced by Mg2+ likely change the stability of aragonite and affect the polymorph selection of CaCO3.
    Preview · Article · Dec 2015
  • Jun Kawano · Satoshi Maeda · Takaya Nagai
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    ABSTRACT: Mg(2+) is considered to play an important role in the formation of calcium carbonate polymorphs; however, how it affects polymorph selection during the early stages of CaCO3 formation is not yet well understood. In the present study, in order to clarify the effect of Mg(2+) on the nucleation of calcium carbonate polymorphs, the stable structures of anhydrous additive-free and Mg-containing calcium carbonate clusters are derived using the anharmonic downward distortion following method, based on quantum chemical calculations. Optimization is performed at the B3LYP/6-31+G(d) level and the solvent effect is induced by the self-consistent reaction field method using the conductor-like polarized continuum calculation model. Calculation results show that incorporating Mg(2+) into clusters can change the clusters' stable configuration. In the case of dimers and trimers, a Mg ion strongly prefers to locate at the centre of the clusters, which suggests that Mg is easy to incorporate into the clusters once it is released from its tight hydration shell. Notably, structures similar to the crystalline phase appear when only four CaCO3 units aggregate into the cluster: in the stable structure of the additive-free CaCO3 tetramer, the arrangement of Ca and CO3 ions is almost the same as that of the calcite structure, while the structure of the Mg-containing CaCO3 tetramer resembles the aragonite structure in the way that CO3 ions are stacked. These results indicate that Mg can play a key role in aragonite formation not only by inhibiting calcite growth but also by directly promoting aragonite nucleation in the early stages of CaCO3 formation.
    No preview · Article · Jan 2015 · Physical Chemistry Chemical Physics
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    ABSTRACT: In situ neutron diffraction measurements combined with the pulsed neutron source at the Japan Proton Accelerator Research Complex (J-PARC) were conducted on high-pressure polymorphs of deuterated portlandite (Ca(OD)(2)) using a Paris Edinburgh cell and a multi-anvil press. The atomic positions including hydrogen for the unquenchable high-pressure phase at room temperature (phase II') were first clarified. The bent hydrogen bonds under high pressure were consistent with results from Raman spectroscopy. The structure of the high-pressure and high-temperature phase (Phase II) was concordant with that observed previously by another group for a recovered sample. The observations elucidate the phase transition mechanism among the polymorphs, which involves the sliding of CaO polyhedral layers, position modulations of Ca atoms, and recombination of Ca-O bonds accompanied by the reorientation of hydrogen to form more stable hydrogen bonds.
    No preview · Article · Oct 2014 · Journal of Solid State Chemistry
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    ABSTRACT: Spin transition and substitution of Fe3+ in Fe3+AlO3-bearing MgSiO3 perovskite (Pv) and post-perovskite (PPv) were examined up to 200 GPa and 165 GPa, respectively, at room temperature by X-ray emission spectroscopy (XES) and XRD. The results of XES and XRD indicate that in Pv high spin (HS) Fe3+ at the dodecahedral (A) site replaces Al at the octahedral (B) site and becomes low spin (LS) between 50 and 70 GPa with pressure, while in PPv LS Fe3+ occupies the B-site and Al occupies the A-site above 80-100 GPa. The Fe3+-Al coupled substitution seems to be at work in both Pv and PPv. Combining these results on Fe3+ with the recent first-principles calculations on Fe2+ in Pv and PPv, the spin transition and substitution of iron in pyrolitic lower mantle minerals are proposed. Further, their effects on iron-partitioning among the lower mantle minerals are discussed.
    Full-text · Article · Mar 2014 · Physics of The Earth and Planetary Interiors
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    ABSTRACT: The silicate perovskite phase relation between CaSiO3 and MnSiO3 was investigated at 35-52 GPa and at 1,800 K using laser-heated diamond anvil cells combined with angle-dispersive synchrotron X-ray diffraction and energy-dispersive X-ray spectroscopic chemical analyses with scanning or transmission electron microscopy. We found that MnSiO3 can be incorporated into CaSiO3 perovskite up to 55, and 20 mol % of CaSiO3 is soluble in MnSiO3 perovskite. The range of 55-80 mol % of MnSiO3 in the CaSiO3-MnSiO3 perovskite system could be immiscible. We also observed that the two perovskite structured phases of the Mn-bearing CaSiO3 and the Ca-bearing MnSiO3 coexisted at these conditions. The Mn-bearing CaSiO3 perovskite has non-cubic symmetry and the Ca-bearing MnSiO3 perovskite has an orthorhombic structure with space group Pbnm. All the perovskite structured phases in the CaSiO3-MnSiO3 system convert to the amorphous phase during pressure release. MnSiO3 is the first chemical component confirmed to show such a superior solid solubility in CaSiO3 perovskite.
    Full-text · Article · Feb 2014 · Physics and Chemistry of Minerals
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    ABSTRACT: Experiments using laser-heated diamond anvil cells combined with synchrotron X-ray diffraction and SEM–EDS chemical analyses have confirmed the existence of a complete solid solution in the MgSiO3–MnSiO3 perovskite system at high pressure and high temperature. The (Mg, Mn)SiO3 perovskite produced is orthorhombic, and a linear relationship between the unit cell parameters of this perovskite and the proportion of MnSiO3 components incorporated seems to obey Vegard’s rule at about 50 GPa. The orthorhombic distortion, judged from the axial ratios of a/b and $ \sqrt{2}\,a/c, $ 2 a / c , monotonically decreases from MgSiO3 to MnSiO3 perovskite at about 50 GPa. The orthorhombic distortion in (Mg0.5, Mn0.5)SiO3 perovskite is almost unchanged with increasing pressure from 30 to 50 GPa. On the other hand, that distortion in (Mg0.9, Mn0.1)SiO3 perovskite increases with pressure. (Mg, Mn)SiO3 perovskite incorporating less than 10 mol% of MnSiO3 component is quenchable. A value of the bulk modulus of 256(2) GPa with a fixed first pressure derivative of four is obtained for (Mg0.9, Mn0.1)SiO3. MnSiO3 is the first chemical component confirmed to form a complete solid solution with MgSiO3 perovskite at the P–T conditions present in the lower mantle.
    Full-text · Article · Jul 2013 · Physics and Chemistry of Minerals
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    ABSTRACT: The skeletal texture and crystal morphology of the massive reef-building coral Porites lobata were observed from the nano- to micrometer scale using an analytical transmission electron microscope (ATEM). The skeletal texture consists of centers of calcification (COCs) and fiber area. Fiber areas contain bundles of needle-like aragonite crystals that are elongated along the crystallographic c-axis and are several hundred nanometers to one micrometer in width and several micrometers in length. The size distribution of aragonite crystals is relatively homogeneous in the fibers. Growth lines are observed sub-perpendicular to the direction of aragonite growth. These growth lines occur in 1-2μm intervals and reflect a periodic contrast in the thickness of an ion-spattered sample and pass through the interior of some aragonite crystals. These observations suggest that the medium filled in the calcification space maintains a CaCO(3)-supersaturated state during fiber growth and that a physical change occurs periodically during the aragonite crystals of the fiber area.
    No preview · Article · Oct 2012 · Journal of Structural Biology
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    ABSTRACT: There are still large discrepancies among the previous reports on the spin transition of iron in Mg–perovskite (Pv). To alleviate this problem, we examined the spin state of Fe3 + in Mg0.85Fe3 +0.15Al0.15Si0.85O3 Pv up to 200 GPa by X-ray emission spectroscopy (XES) and X-ray diffraction (XRD). The gradual decrease of the high spin (HS) ratio of Fe3 + by low temperature annealing of the samples above ~ 60 GPa in XES and the change of the trend of unit cell volumes with pressure by annealing at 50–60 GPa in XRD indicate that Fe3 + occupies the A-site and is HS below ~ 50 GPa but above 50–60 GPa it gradually replaces Al at the B-site through cation exchange reaction by annealing and becomes low spin (LS), while Fe3 + remaining at the A-site is HS up to 200 GPa. This means that the spin state of Fe3 + depends on Fe3 + occupancies between the A- and B-sites and these Fe3 + occupancies are strongly controlled by the synthesis condition and annealing temperature of the samples through the cation exchange reaction. The present results combined with the previous reports indicate that in Al-bearing Mg–Pv in the lower mantle Fe2 + occupies the A-site and remains HS for the whole lower mantle, while Fe3 + occupies the A-site and is HS below ~ 50 GPa but above 50–60 GPa it replaces Al at the B-site and becomes LS, on the assumption that spin transition pressure of Fe2 + at the A-site is higher than that of Fe3 + at the same site.
    No preview · Article · Feb 2012 · Earth and Planetary Science Letters
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    ABSTRACT: The pressure responses of portlandite and the isotope effect on the phase transition were investigated at room temperature from single-crystal Raman and IR spectra and from powder X-ray diffraction using diamond anvil cells under quasi-hydrostatic conditions in a helium pressure-transmitting medium. Phase transformation and subsequent peak broadening (partial amorphization) observed from the Raman and IR spectra of Ca(OH)2 occurred at lower pressures than those of Ca(OD)2. In contrast, no isotope effect was found on the volume and axial compressions observed from powder X-ray diffraction patterns. X-ray diffraction lines attributable to the high-pressure phase remained up to 28.5GPa, suggesting no total amorphization in a helium pressure medium within the examined pressure region. These results suggest that the H–D isotope effect is engendered in the local environment surrounding H(D) atoms. Moreover, the ratio of sample-to-methanol–ethanol pressure medium (i.e., packing density) in the sample chamber had a significant effect on the increase in the half widths of the diffraction lines, even at pressures below the hydrostatic limit of the pressure medium. KeywordsPortlandite–Isotope effect–Phase transition–Hydrostaticity–Hydrogen bonding
    No preview · Article · Dec 2011 · Physics and Chemistry of Minerals
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    ABSTRACT: The El Niño/Southern Oscillation (ENSO) system during the Pliocene warm period (PWP; 3-5 million years ago) may have existed in a permanent El Niño state with a sharply reduced zonal sea surface temperature (SST) gradient in the equatorial Pacific Ocean. This suggests that during the PWP, when global mean temperatures and atmospheric carbon dioxide concentrations were similar to those projected for near-term climate change, ENSO variability--and related global climate teleconnections-could have been radically different from that today. Yet, owing to a lack of observational evidence on seasonal and interannual SST variability from crucial low-latitude sites, this fundamental climate characteristic of the PWP remains controversial. Here we show that permanent El Niño conditions did not exist during the PWP. Our spectral analysis of the δ(18)O SST and salinity proxy, extracted from two 35-year, monthly resolved PWP Porites corals in the Philippines, reveals variability that is similar to present ENSO variation. Although our fossil corals cannot be directly compared with modern ENSO records, two lines of evidence suggest that Philippine corals are appropriate ENSO proxies. First, δ(18)O anomalies from a nearby live Porites coral are correlated with modern records of ENSO variability. Second, negative-δ(18)O events in the fossil corals closely resemble the decreases in δ(18)O seen in the live coral during El Niño events. Prior research advocating a permanent El Niño state may have been limited by the coarse resolution of many SST proxies, whereas our coral-based analysis identifies climate variability at the temporal scale required to resolve ENSO structure firmly.
    Full-text · Article · Mar 2011 · Nature
  • Takaya Nagai · Daisuke Hamane · Kiyoshi Fujino
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    ABSTRACT: MgSiO3 dominant perovskite is believed to be the most abundant constituent mineral in the Earth’s lower mantle. Generally minerals form solid solutions and their nature should affect on physical properties of minerals. In this paper, we will introduce our recent studies about incorporation mechanism of FeAlO3 component into MgSiO3 perovskite and its crystal chemistry.
    No preview · Article · Jan 2011
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    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    No preview · Article · Mar 2010 · ChemInform
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    ABSTRACT: Angle dispersive powder X-ray diffraction experiments using a flat imaging plate (IP) are one of the most popular methods in high-pressure material science. In order to support such experiments, we developed two software, IPAnalyzer and PDIndexer. IPAnalyzer can convert a two-dimensional Debye-ring pattern to one-dimensional (Bragg-Brentano) geometry. IPAnalyzer can also calibrate experimental parameters (wave length, camera length, and so on) automatically. PDIndexer can display the converted pattern(s) and diffraction peaks calculated for any crystals.
    No preview · Article · Jan 2010 · The Review of High Pressure Science and Technology
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    ABSTRACT: High pressure and high temperature experiments on CaSiO3, FeSiO3, MnSiO3 and CoSiO3 using a laser-heated diamond anvil cell combined with synchrotron X-ray diffraction were conducted to explore the perovskite structure of these compounds and the transition to the post-perovskite structure. The experimental results revealed that MnSiO3 has a perovskite structure from relatively low pressure (ca. 20 GPa) similarly to CaSiO3, while the stable forms of FeSiO3 and CoSiO3 are mixtures of mono-oxide (NaCl structure) + high pressure polymorph of SiO2 even at very high pressure and temperature (149 GPa and 1800 K for FeSiO3 and 79 GPa and 2000 K for CoSiO3). This strongly suggests that the crystal field stabilization energy (CFSE) of Fe2+ with six 3d electrons and Co2+ with seven 3d electrons at the octahedral site of mono-oxides favors a mixture of mono-oxide + SiO2 over perovskite where Fe2+ and Co2+ would occupy the distorted dodecahedral sites having a smaller CFSE (Mn2+ has five 3d electrons and has no CFSE). The structural characteristics that the orthorhombic distortion of MnSiO3 perovskite decreases with pressure and the tolerance factor of CaSiO3 perovskite (0.99) is far from the orthorhombic range suggest that both MnSiO3 and CaSiO3 perovskites will not transform to the CaIrO3-type post-perovskite structure even at the Earth's core–mantle boundary conditions, although CaSiO3 perovskite has a potentiality to transform to the CaIrO3-type post-perovskite structure at still higher pressure as long as another type of transformation does not occur.
    Full-text · Article · Dec 2009 · Physics of The Earth and Planetary Interiors
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    ABSTRACT: The compression behaviors of delta-AlOOH and delta-AlOOD were investigated under quasi-hydrostatic conditions at pressures Lip to 63.5 and 34.9 GPa, respectively, using results from synchrotron X-ray diffraction experiments conducted at ambient temperature. Because of the geometric isotope effect, at ambient pressure, the a and b axes of delta-AlOOD, which define the plane in which the hydrogen bond lies, are longer than those of delta-AOOH. Under increasing pressure, the a and b axes of delta-AlOOH stiffen at 10 GPa, although the c axis shows no marked change. Identical behavior was found in delta-AlOOD, but the change in compressibility was observed at a slightly higher pressure of 12 GPa. Axial ratios a/c and b/c first decrease rapidly with increasing pressure, then begin to increase at pressures >10 GPa in delta-AlOOH and >12 GPa in delta-AlOOD. At these pressures, the pressure dependence of a/b also changes from increasing to decreasing. The unit-cell volumes of delta-AlOOH and delta-AlOOD become slightly less compressible at high pressures. Assuming K(0)(') = 4, the calculated bulk moduli of delta-AlOOH below and above 10 GPa are 152(2) and 219(3) GPa, respectively. Those of delta-AlOOD below and above 12 GPa are 151(1) and 207(2) GPa, respectively.
    No preview · Article · Aug 2009 · American Mineralogist
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    ABSTRACT: It is expected that high-pressure material science and the investigation of the Earth's interior will progress greatly using the high-flux pulse neutrons of J-PARC. In this article, we introduce our plans for in situ neutron powder diffraction experiments under high pressure at J-PARC. The use of three different types of high-pressure devices is planned; a Paris–Edinburgh cell, a new opposed-anvil cell with a nano-polycrystalline diamond, and a cubic anvil high-pressure apparatus. These devices will be brought to the neutron powder diffraction beamlines to conduct a “day-one” high-pressure experiment. For the next stage of research, we propose construction of a dedicated beamline for high-pressure material science. Its conceptual designs are also introduced here.
    No preview · Article · Feb 2009 · Nuclear Instruments and Methods in Physics Research Section A Accelerators Spectrometers Detectors and Associated Equipment
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    ABSTRACT: It is great exciting news for our high pressure science community in Japan that the first pulsed neutron beams were delivered to J-PARC Materials & Life Science Experimental Facility (MLF) on May 30th, 2008. We believe that the newly dedicated pulsed neutron beams will open a new window in the high-pressure science world. Over the past 7 years, we have prepared some projects to build a high pressure and high temperature material science beamline in the MLF. In this article, we will give a brief overview of the progress of those projects and also introduce a newly designed high-pressure cell and a neutron focusing mirror for in-situ neutron diffraction experiments at high pressure and high temrjerature.
    No preview · Article · Jan 2009 · The Review of High Pressure Science and Technology
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    ABSTRACT: A method was proposed for measuring infrared absorption spectra at high pressure under quasi-hydrostatic pressure conditions. Two KBr micro-pellets were prepared as samples, and reference materials were charged in a diamond anvil cell, applying helium as the pressure-transmitting medium. Using this method, the quasi-hydrostatic pressure condition was retained up to approximately 20 GPa. Furthermore, hydrostaticity was much better than conventional pressure-transmitting media used for infrared spectroscopy. Infrared absorption spectra of α -FeOOH at high pressure were measured using the KBr micro-pellet method with a helium pressure-transmitting medium. Downshift of the OH stretching vibration was observed with increasing pressure. Use of the KBr micro-pellet method for infrared absorption spectroscopy at high pressure is a complementary experimental technique to neutron diffraction at high pressure for studying the pressure response of hydrogen bonds.
    No preview · Article · Sep 2008 · High Pressure Research
  • Yusuke Seto · Daisuke Hamane · Takaya Nagai · Kiyoshi Fujino
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    ABSTRACT: We report on high-pressure and high-temperature experiments involving carbonates and silicates at 30–80GPa and 1,600–3,200K, corresponding to depths within the Earth of approximately 800–2,200km. The experiments are intended to represent the decomposition process of carbonates contained within oceanic plates subducted into the lower mantle. In basaltic composition, CaCO3 (calcite and aragonite), the major carbonate phase in marine sediments, is altered into MgCO3 (magnesite) via reactions with Mg-bearing silicates under conditions that are 200–300°C colder than the mantle geotherm. With increasing temperature and pressure, the magnesite decomposes into an assemblage of CO2+perovskite via reactions with SiO2. Magnesite is not the only host phase for subducted carbon—solid CO2 also carries carbon in the lower mantle. Furthermore, CO2 itself breaks down to diamond and oxygen under geotherm conditions over 70GPa, which might imply a possible mechanism for diamond formation in the lower mantle.
    No preview · Article · May 2008 · Physics and Chemistry of Minerals
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    ABSTRACT: The high-pressure phase relation of MnSiO3 was examined up to 85 GPa and 2600 K using a laser-heated diamond-anvil cell combined with synchrotron radiation. MnSiO3 garnet decomposes into a mixture of MnO with a rock-salt structure (B1) + SiO2 stishovite at pressures higher than ~20 GPa and temperatures higher than ~1200 K. However, MnO (B1) + SiO2 stishovite further transforms to a perovskite structure with increasing pressure. The phase boundary between these structures is positive in the pressure-temperature diagram. The triple point of garnet, MnO + SiO2 and perovskite in the pressure-temperature diagram is ~20 GPa and 1200 K. MnSiO3 perovskite is orthorhombic, and consistent with space group Pbnm, both at high pressure and high temperature and at high pressure and room temperature, but becomes amorphous during decompression. The refined cell parameters of MnSiO3 perovskite at 85 GPa and 2600 K are a = 4.616(2) Å, b = 4.653(2) Å, c = 6.574(3) Å, and V = 141.2(2) Å3. The a/b ratio increases (approaches 1) with pressure and temperature, while the √2a/c ratio remains nearly constant (<1). This indicates that the orthorhombic distortion decreases and the structure tends toward a tetragonal perovskite with increasing pressure and temperature.
    No preview · Article · Apr 2008 · American Mineralogist

Publication Stats

528 Citations
119.12 Total Impact Points

Institutions

  • 2004-2015
    • Hokkaido University
      • • Faculty of Science
      • • Department of Natural History Sciences
      • • Graduate School of Science
      Sapporo, Hokkaidō, Japan
  • 1997-2010
    • Osaka University
      • • Department of Earth and Space Science
      • • Graduate School of Science
      Suika, Ōsaka, Japan
  • 2001
    • State University of New York
      New York, New York, United States