Magma & Crystal Chemistry Group Page

Magma & Crystal Chemistry Group

About the Group:

The aims of this group are to promote researches on the structure and physical properties of magmas, fluids and minerals through comprehensive spectroscopic measurements, high pressure-high temperature experiments, in-situ high pressure-high temperature observations using synchrontron radiations, and computer simulations. Members of the group formally belong to either the "Experimental Planetary Physics Division" or the "Promotion of International Collaborative Research Division". For more details of the formal affilliation of individual members, please click here.

Members

Faculty members:

Kanzaki, Masami, Professor [personal page]

Xue, Xianyu, Associate Professor [personal page]

Yamashita, Shigeru, Associate Professor (temporarily staying Geophysical lab this winter)[personal page]

Postdoctoral fellows:

Yachi, Yusuke[Info]
(super-technician)

Graduate students:

Visiting scientists:

Bjorn Mysen (Geophysical Lab, Carnegie Institution of Washington)

Alumni:

Shimoda, Keiji (former posdoc, now moved to Hiroshima University

Malfait, Wim (former posdoc, now back to ETH)

Fukui, Hiroshi (former posdoc -> SPring-8 -> University of Hyogo)

Xiang Wu (former visiting scientist -> Bayerisches Geoinstitut -> Peking University)

Tsujimura, Tomoyuki (former graduate student, now working at AGC)

Researches

Researches in the Magma & Crystal Chemistry Group focus on the structure and physical properties of minerals, melts, glasses and fluids as described below.

Local Structures of Glasses: Spectroscopic techniues, in particular NMR and Raman, are being used to investigate the local structure of glasses (quenched melts) synthesized at ambient pressure as well as high pressures using internally heated gas pressure vessel (IHPV) and multi-anvil press. NMR has been found to be a powerful technique to probe the complicated structures of amorphous materials , because it provides information about local structures around indivial elements (nuclei) regardless of whether there are long-range orders or not, and can also yield direct connectivity information by manipulating the dipolar interactions among spins through advanced one- and two- dimensional NMR experiments. Recently, we have made much progress in unraveling the dissolution mechanisms of water in silicate and aluminosilicate melts by fully exploring the potential of advanced NMR techniques. For more details, please see the publication list below.

Local Structures of Minerals: Although X-ray diffraction (XRD) is the main tool for structural determinations of crystalline materials, there are several important issues that cannot be uniquely resolved by XRD. These include Mg-Al-Si order/disorder and proton distributions. On the other hand, NMR has been known to be the most powerful technique in obtaining quantitative information on these issues. Vibrational spectroscopy (IR & Raman) is complementary in the sense that although their spectral interpretations are less unique, they can provide information about spatial distributions as a result of superior spatial resolution, and are also amenible to in-situ observations at high pressure and high temperature. Currently, we are systematically investigating the Si-Al-Mg order/disorder and proton distribution/ hydrogen bonding in all major mantal minerals (hydrous and nominally anhydrous) using NMR and Raman spectroscopy. In-situ Raman measurements on minerals under high pressure using DAC is also planned to be carried out in the near future.

Computational Approach: We are also conducting computational studies of minerals, melts and mineral-water interaction to complement and guide experimental work. The techniques applied include molecular dynamics (MD) calculations (both classical and ab initio), and ab initio quantum mechanical calculations using software packages such as Gaussian03, GAMESS and WIEN2K. For example, we have found ab initio molecular orbital calculations a particularly convenient tool for predicating structure - NMR parameter correlations. We also routinely perform MD and first-principles calculations to check and predict structure and physical properties of crystalline phases that are under investigation by parallel experimental approach. The combined experimental and computational approach is becoming increasingly important for the study of earth materials, and expertise in both aspects is one of the characteristics of our group.

In-situ Observations of Fluids/Melts Under High Pressure and Temperature: Although NMR provides the richest information about local structures on glasses, it is difficult to extract similar information in-situ on the melts/fluids at high temperature/pressure. Therefore, we utilize Raman and FT-IR spectroscopy for in-situ observations of melts/fluids under high pressure and temperature. We have succeeded in-situ Raman and IR measurements under P-T conditions up to several GPa and 800C using an externally heated DAC, and is currently investigating the structure of hydrous silicate melts.

In-situ Observations of the Critical Behavior of Fluid-Melt System: On the Earth system, two types of fluids are present, melt and water. With increasing high pressure, both the solubility of water in the melt and the solubility of silicate in the fluid increase. Beyond certain pressure (the so-called critical end point), complete miscibility betwen the two is expected to occur. Above the critical pressure, melting of water-bearing rocks produce a single critical fluid phase, rather than melt+fluid. This phenomenon may have significant bearing on the geochemical behavior of elements in the subducted slabs. For the observation of critical behavior of fluid-melt system below 1000C, the externally heated DAC described above may be used. For higher-temperture experiments, as are requried for basalt- and perodotite- water system, we have developed a high-pressure X-ray radiography technique using synchrontron radiation with multi-anvil press several years ago. We have succeeded in measuring the critical end point for several silicate-water systems. This project is being continued at present.

In-situ physical property measurement of melts under high P-T: We are also using the above high-pressure X-ray radiography technique to determine the physical properties of silicate melts. For example, we were the first to design the in-situ viscosity measurement method for silicate melts by observing the settling of metal spheres in the sample in a multi-anvil high-pressure apparatus.

High-pressure X-ray Raman Spectroscopy: X-ray Raman spectroscopy is a promising new technique that may provide unique in-situ information about the local structures around light elements in minerals and glasses under high pressure. Currently, we are developing this technique and applying it to the study the local structures around O and Si in silicate glasses and minerals at SPring-8.

Phase Equilibria of High-pressure Hydrous Silicate Phases: It is widely believed that water is being carried down the subducted slab to the deep earth, resulting in the formation of hydrous minerals at high pressure. The dehydration reaction boundary of hydrous phases reflect the physical properties of fluids at high pressure, rendering the determination of the former an unique method for obtaining indirect information of the latter. Currently, we are carrying out quench experiments using multi-anvil press to investigate the dehydration reaction and phase equilibria for important high-pressuree hydrous minerals. In addition, we are also performing in-situ XRD observation experiments at SPring-8 to determine the phase boundary of a new high-pressure phase of topaz-OH, which was first discovered by us by NMR/Raman spectroscopy.

Facilities

We use various spectroscopic techniques and ambient pressure and high pressure synthesis equipments for researches in the Magma & Crystal Chemistry Group. Some of the equipments that belong to the group are listed below. Most of them are accesible for collaborative researches. For more details, please click the links below.

High-resolution solid-state nuclear magnetic resonance spectrometer (NMR)

Micro-Raman spectrometer

Micro-FTIR spectrometer

Externally heated diamond anvil cell (2GPa, 800C)

YAG laser heating system and diamond anvil cell (100GPa, 3000C)

Piston cyclindar high-pressrue apparatus (2GPa, 1500C)

Internally heated gas pressure vessel (200MPa, 1500C)

Cold-seal hydrothermal apparatus (100MPa,600C)

FZ furnace for single-crystal growth

Wire heating device for high T Raman (in Japanese)

Resources

X-ray powder diffraction patterns of high-pressure minerals, and crystal structure data

NMR Database of minerals

Summary of in-situ study during COE21 program (pdf)

Applications

We are accepting graduate students and postdoctral fellows. We are also welcome researchers to conduct cooperative study with us. We can provide traveling and staying fee. Currently "International Intern Student Program" is open for application. If you are interested in our program, please click here.

Publications

Recent Publications (Since 2004):

Xue, X. and Kanzaki, M., Proton distributions and hydrogen bonding in crystalline and glassy hydrous silicates and related inorganic materials: Insights from high-resolution solid-state nuclear magnetic resonance spectroscopy, J. Am. Ceram. Soc., 92 (12), 2803-2830, 2009.

Xue, X., Zhai, S., Kanzaki, M., Si-Al distribution in high-pressure CaAl₄Si₂O₁₁ phase: a ²⁹Si and ²⁷Al NMR study. Am. Min., 94, 1739-1742, 2009.

X. Wu, G. Steinle-Neuman, S. Qin, M. Kanzaki and L. Dubrovinsky, Pressure-induced phase transitions of AX₂-type iron pnictides: ab initio study, Journal of Physics: Condensed Matter, 21, 185403, 2009

X. Wu, M. Kanzaki, S. Qin, G. Steinle-Neumannand L. Dubrovinsky, Structural study of FeP₂ at high pressure, High Pressure Research, 29, 235-244, 2009

V.V. Brazhkin, M. Kanzaki, K. Funakoshi and Y. Katayama, Viscosity behavior spanning four orders of magnitude in As-S melts under high pressure, Phys. Rev. Lett., 102, 115901, 2009

Xue, X., Water speciation in hydrous silicate and aluminosilicate glasses: Direct evidence from ²⁹Si-¹H and ²⁷Al-¹H double-resonance NMR. Am. Min., 94, 395-398, 2009.

H. Fukui, M. Kanzaki, N. Hiraoka and Y.Q. Cai, X-ray Raman scattering for structural investigation of silica/silicate minerals, Phys. Chem. Minerals, 36, 171-181, 2009.

M. Kanzaki, Elastic wave velocities and Raman shift of MORB glasses at high pressures-Comment, Journal of Mineralogical Petrological Sciences, 103, 427-428, 2008.

Behrens, H., Yamashita, S., Water speciation in hydrous sodium tetrasilicate and hexasilicate melts: Constraint from high temperature NIR spectroscopy, Chem. Geol., 256, 306-315, 2008

Mysen, B.O., Yamashita, S., Chertkova, N., Solubility and solution mechanisms of NOH volatiles in silicate melts at high pressure and temperature-amine groups and hydrogen fugacity, Am. Min., 93, 1760-1770, 2008

Yamashita, S., Behrens, H., Schmidt, B.C., Dupree, R., Water speciation in sodium silicate glasses based on NIR and NMR spectroscopy, Chem. Geol., 256, 231-241, 2008

H. Fukui, M. Kanzaki, N. Hiraoka and Y.Q. Cai, Coordination environment of silicon in silica glass up to 74 GPa: An X-ray Raman scattering study at the silicon L edge, Phys. Rev. B, 78, 012203, 2008

X. Xue, M. Kanzaki, and A. Shatskiy, Dense hydrous magnesium silicates, phase D and superhydrous B: New structural constraints from one- and two- dimensional ²⁹Si and ¹H NMR, Am. Mineral., 93, 1099-1111, 2008.

X. Xue and M. Kanzaki, Structure of hydrous aluminosilicate glasses along the diopside-anorthite join: a comprehensive one- and two-dimentional ¹H and ²⁷Al NMR study, Geochim. Cosmochim. Acta, 72, 2331-2348, 2008.

H. Fukui, X-ray Raman scattering: Application to materials of the Earth's Interior (in Japanese), Rev. of High Pressure Sci. Tech., 18, No.1, 31-37 (2008)

V.V.Brazhkin, K. Funakoshi, M. Kanzaki and Y. Katayama, Nonviscous metallic Se, Phys. Rev. Lett., 99, 245901 (2007)

X. Xue and M. Kanzaki, High-Pressure delta-Al(OH)₃ and delta-AlOOH Phases and Isostructural Hydroxides/Oxyhydroxides: New Structural Insights from High-Resolution ^1H and ²⁷Al NMR, Journal of Physical Chemistry B, Accepted.

Fukui, H., Huotari, S., Andrault, D., Kawamoto, T., Oxygen K-edge fine structures of water by x-ray Raman scattering spectroscopy under pressure conditions. Jour. Chem. Phys., 127, 134502-134506, 2007.

Kenji Mibe, Masami, Kanzaki, Tatsuhiko Kawamoto, Kyoko N. Matsukage, Yingwei Fei and Shigeaki Ono, Second critical endpoint in the peridotite-H₂O system, J. Geophys. Res., 112, B03201, doi:10.1029/2005JB004125, 2007.

Lin, J.F., Fukui, H., Prendergast, D., Okuchi, T., Cai, Y.Q., Hiraoka, N., Yoo, C.S., Trave, A., Eng, P., Hu, M.Y., Chow, P., Electronic bonding transition in compressed SiO₂ glass. Phys. Rev. B, 75, 012201, 2007.

X. Xue and M. Kanzaki, Al coordination and water speciation in hydrous aluminosilicate glasses: Direct evidence from high-resolution heteronuclear ¹H-²⁷Al correlation NMR, Solid State NMR, 31, 10-27, 2007.

Yoshino, T., Matsuzaki, T., Yamashita, S., Katsura, T., Hydrous olivine unable to account for conductivity anomaly at the top of the asthenosphere, Nature, 443, 973-976, 2006.

X. Xue and M. Kanzaki, Depolymerization effect of water in aluminosilicate glasses: direct evidence from ¹H-²⁷Al heteronuclear correlation NMR, Am. Mineral., 91, 1922-1926, 2006.

X. Xue, M. Kanzaki, H. Fukui, E. Ito, and T. Hashimoto, Cation order and hydrogen bonding of high-pressure phases in the Al₂O₃-SiO₂-H₂O system: An NMR and Raman study, Am. Mineral., 91, 850-861, 2006.

Sano, T., Yamashita, S., Experimental petrology of basement lavas form Ocean Drilling Program Leg 192: implications for differentiation processes in Ontong Java Plateau magmas, in: Fitton J.G, Mahoney, J.J., Walllace, P. J. & Saunders, A.D. (eds.), Origin & Evolution of the Ontong Java Plateau, Geological Society, London, Special Publication 229, 185--218, 2004

K. Mibe, M. Kanzaki, T. Kawamoto, K.N. Matsukage, Y. Fei and S. Ono, Determination of the second critical end point in silicate-H₂O systems using high-pressure and high-temperature X-ray radiography, Geochim. Cosmochim. Acta., 68, 5189-5195, 2004.

T. Tsujimura, X. Xue, M. Kanzaki and M.J. Walter, Sulfur speciation and network structural changes in sodium silicate glasses: Constraints from NMR and Raman spectroscopy, Geochim. Cosmochim. Acta., 68, 5081-5101, 2004.

X. Xue and M. Kanzaki, Dissolution mechanisms of water in depolymerized silicate melts: Constraints from ¹H and ²⁹Si NMR spectroscopy and ab initio calculations, Geochim. Cosmochim. Acta., 68, 5027-5057, 2004.

X. Xue, M. Kanzaki. D.R. Neuville and T. Kawamoto, Structure and properties of silicate melts and fluids, Geochim. Cosmochim. Acta., 68, 5011-5012, 2004.