Application of Synchrotron X-ray Radiation
to Earth and Planetary Sciences
Eiji Ohtani
Graduate School of Science,Tohoku University

Abundance, Si=106

Solar abundance: A large amount of light elements, H, He,C, O, N, and elements forming terrestrial planets, Si, Mg, Fe.

Atomic number

Terrestrial planets, Gas Giants, Ice Giants……

Mars

EarthVenus
Titan

Icy satellites of outer planets

Gallireosatellites

Application of Synchrotron X-ray radiation
to Earth and Planetary Sciences
1. X-ray diffraction and spectroscopic studies under theconditions of the center of the Earth, i.e., 5000-6000 K at 365
GPa
2. Some volatile components such as H2, H2O, CH3, and NH4
are also important materials relevant to the internal
structures of the objects in the outer solar system.
3. Structures and physical properties of silicate liquids(magmas) and metallic liquids (outer core) at high pressure:liquid miscibility, equation of state, viscosity, and interfacial
energy of the liquids.
4. Studies on fracturing and rheological properties of geomaterials. Development of imaging techniques such as X-ray
radiography and tomography under the deformed andstressed conditions. The imaging and tomography are also
applied in volcanology
5. X-ray imaging and diffraction of micro-samples such ascosmic dusts: Recovered samples from the Stardust mission.
Imaging and tomography are also used for observation of themicro-textures of the samples with geological interests.

High Pressure Generation Procedure
Cell configuration for TEL 3.0 mm(experiments at 20-25 GPa)

MAP

2θ
X-ray

W-Re Thermocouple

DAC4

Application of Synchrotron X-ray
radiation to Earth and Planetary Sciences
1. X-ray diffraction and spectroscopic studies of Iron andSilicates to the conditions of the center of the Earth, i.e., 50006000 K at 365 GPa
2. Some volatile components such as H2, H2O, C, CH3, and NH4
are also important materials relevant to the internal
structures of the objects in the outer solar system.
3. Structures and physical properties of silicate liquids(magmas) and metallic liquids (outer core) at high pressure:liquid miscibility, equation of state, viscosity, and interfacial
energy of the liquids.
4. Studies on fracturing and rheological properties of geomaterials. Development of imaging techniques such as X-ray
radiography and tomography under the deformed andstressed conditions. The imaging and tomography are also
applied in volcanology

Iron Alloys and Planetary CoreThe Earthʼs Core: A frontier in Earth Science
Hot spot
TrenchRidge

From Surface to Core: Global transportof Earthʼs materials

LiquidOuterCoreSolidInnerCore
２

PREM: Preliminary Reference Earth Model

Primary observationfrom seismology isVp and Vs: Difficult
to determine
experimentally

Crust0Mantle
2000

Outer core
4000

Inner core6000

Depth, km
３

The core density: lower by 7 - 10 % than that of pureiron (Anderson and Issak, 2002; Shanker et al., 2004).
Dissolution of light elements, such as S, O, H, and Si in iron
may explain the density of the core.

４Temperature
difference

Temperature vatiation can be dominant at
the shallow depths of the mantle, but ….

dV/dX, X= Temp, Chem.

(after Karato, 2008)
Effect of temperature
Mantle Core
Effect of Chemistry

MantleTZ
LM
UM

Chemicaldifference?

CoreOCIC

Depth, Pressure

Temperature variation is dominant atshallow depths.
Chemical effects can be dominant athigh pressure.
５Volume_hcp cm3/mol

22Fe-3.4wt%Si
Fe-9.8wt%Ni-4wt%Si(Hirao et al., 2005)

20

4000K

7000K

Volume (A)Hcp-Fe0.9Ni0.1 300K

(Hirao, Ohtani et al., 2005;
Asanuma, Ohtani et al., 2008 )

1816

14

12050

100

150200250

Pressure (GPa)Temperature effect is small, whereas chemical effect is large
under the core conditions.

300

350

400

Center ofthe Earth.&/$0$'(#$01'$21'3

Double sided laser heating
diamond cell,-./#")01%!"#$%&'(")*+'*0&(2"13*.#%,4"&(*+5367,"/3'(88,"2&(*+#$%&'()*+!",-Ultrahigh pressure and temperature of the Earth’s core
Intensive efforts to achieve these extreme conditions
DAC technology + Synchrotron X-ray source(e.g., Sakai et al., 2006; Hirao et al., 2006; Kuwayama et al., 2007; Asanuma etal., 2008).

Fe3.4wt.%SiHCP

BCC

FeNi alloy

Dubrovinsky et al. (2007)

Our result: Asanuma et al. (2008)

１４

Several methods to determine Seismic Velocity
Ultrasonic measurement MHz (MAP, e.g., Higo et al., 2007): and GHz (DAC,Giga-Hertz method, Jacobsen et al., 2007),
Brillouin scattering spectroscopy (Murakami et al., 2008),
IXS (Fiquet et al., 2004),
NRIXS (e.g., Sturhahn, 2000).

１６Badro et al. (2007) IXS studies of FeS2,FeSi, FeO, FeS, Fe

PREM inner core
PREM Outer core

FeS2FeSi

200 GPa

FeO

Fe-shock
Fe static

FeS

Inner core: Fe2.3% Si
Outer core: 2.8% Si,5.3% O
Badro st al. (2007)

ESRF
ID16, ID28

Behavior of Light Element
compounds in Earth andPlanets
Hydrogen Bond at High PressureBehavior of Hydrogen: New hydrous
phaseδ-AlOOH
Synthesized by δ-AlOOH (Suzuki.etal.2000)
Sructural analysis (Kudoh et al. 2004).
ａ＝4.6975（８）Å ，ｂ＝4.2060（6）Å ，ｃ＝2.8327Å，Ｖ＝55.97（1） Å 3，Space
group Ｒ2ｎｍ; density 3.533g/cm3

Structuralcharacteristics
Similarity to high pressurepolymorph of post-stishovite
phase, CaCl2 type structure
Ohtani et al.(2001)

Stability ofδ-AlOOH
STABILITY FIELD•d-AlOOH is stable in therange from 37 - 134 GPa, up
to 2300 K•

PtHx is stable at pressure
above 80GPa, whereas dAlOOH and Ir are stable athigh pressure.

•d-AlOOH is stable up to thecore-mantle boundary. Thus,
hydrogen can be transported
to the core. Phase Egg,AlSiO3OH, which
decomposes into d-AlOOHand stishovite is observed asinclusions in diamond (Wirthet al., 2007).

Sano, Ohtani, et al. (2007)

O-D distance and O-O distanceO-D, O-H distance (Å)

NEUTRON DIFFRACTION

Ab initio calc.

Sano et al.(2008)

Symmetrization of O-H bond in Ice

INTRODUCTION< 氷の相図 >< Ice VIII >< Ice VII >Lin et al., 2006

High pressure Ice in Lower mantle??

Jupitor

UranusSaturnNeptuneTemperature,Mantle

Cored-AlOOHis stable atleast to 180
GPa

135 GPa
3000 K330 GPa
6000 K
310 GPa
5000 K

H2He
H2O
CH3
NH4Pressure,

135 GPa and 3000K at the core-mantle boundary,
310 GPa and ~5000K at inner core boundary,
330 GPa and ~6000K at the center of the Earth.
１０Temperature, K

Upper mantle

SD-MAP

TZ

Lower mantle

Outercore

Innercore

LHDAC

CAP
DAC

Pressure, GPa

374 GPa
700 K

Application of Synchrotron X-ray radiation to Geosciences

1. X-ray diffraction and spectroscopic studies under theconditions of the center of the Earth, i.e., 5000-6000 K at 365GPa
2. Some volatile components such as H2, H2O, CH3, and NH4
are also important materials relevant to the internal
structures of the objects in the outer solar system.
3. Structures and physical properties of silicate liquids(magmas) and metallic liquids (outer core) at high pressure:liquid miscibility, equation of state, viscosity, and interfacial
energy of the liquids.
4. Studies on fracturing and rheological properties of geomaterials. Development of imaging techniques such as X-ray
radiography and tomography under the deformed andstressed conditions. The imaging and tomography are also
applied in volcanology

Melts, Magmas, and Volcanic activities
and Planetary Molten Cores
・Viscosity measurement offalling sphere X-ray
radiography
High Pressure
Properties of Magmas

Planetary core formation

・Liquid immisibility, Liquidliquid Transitions
By X-ray imaging
・Measurement of Liquid
Density by X-ray imaging
・Interfacial energy at highpressure by X-ray imaging and3D-tomogrphy

X-ray Radiography and Tomography at high pressure:
Application of multianvil press
Radiography
Micro-tomography

PF BL14C(MAX-III)
700 tonSPring-8 BL04B1(SPEED-1500)
1500 ton

APS BL-BMD13250 ton

Multianvil
SPEED-MkIIat Spring-8
MAX-III for Deformation
CubicAnvil
Press (D-CAP)
press

SPEED 1500 at Spring-8

CCDcamera
MAX-III
apparatus installed at PF
X-ray CCDcamera

MAX80 at Photon Factory

Ge-SSD

X-ray intensifier

white X-ray

D-CAP（Deformation cubicanvil GB)

Viscosity measurement of fallingsphere X-ray radiography

Fast CCD camera

Large volume press

Lense

Secondstage anvil
PF #14 VW
White X-ray

High Pressure Cell

First stage anvil

MAX-III @BL-14C2

MirrorFast Video capturing
White X-ray

X-ray Radiography

PF-BL14C2

Viscosity of Silicate
melt at high pressure
by Falling SphereRadiography

Liquid immisibility, Liquid-liquidTransitions

High resolution CCD Camera

High Pressure apparatus

Secondstage anvil
PF #14 VW
MonochromaticLenseMirror

High Pressure cell

25 keV （magma）
30-40 keV （Fe-alloy）
First stage anvil

MAX-III @BL-14C2(GSO, LSO)

Imaging of Fe-O-S melt：Liquid immiscibility in the Fe-O-S
system: Applications to the cores of planets and satellites, such
as Mars and Ganymede
In situ observation is essential for two-liquids phase relations

Tsuno et al. (2007)

Measurement of Liquid Density
by X-ray imaging CCD Camera
Large volume press

Lens

SecondStage anvil
PF#14 VW
Monochro.
単色Ｘ線
beamMirror

High pressure cell

25 keV (magmas)
30-40 keV （Fe-alloys)
First stage anvil
Magma

MAX-III @BL-14C2(GSO, LSO)

Merit of Imaging method
・Short time for measurement
・higher pressureHP and HT X-ray micro-tomography

High pressure tomography system at APS Beamline: BMD13

X-ray radiograph using Toroidal anvil cellcompression

Fig. 6 Toroidal anvil and cell assembly

Fig. 7 Toroidal cell
assembly

Rotation
A step of 0.5o along thevertical axis

Experimental conditions
Pressure: 0.95 GPa (40ton)
Exposure time for imaging: 3 sec.
Image analysis
Image reconstruction: Tomo_display
3D image viewer: Blob3D

ResultsRadiography image Interface

3D tomography image

Tomo-slice

1027K

1253K

1293K

3D tomography image“apparent” interfacial tension of Ni-S liquid at 1027 K of 357 mN/m is a result fromthe non-textural equilibirum or silicate partial melt sample. The “true” interfacial
tensions are 414 mN/m at 1253 K and 336 mN/m at 1293 K. Interfacial tension of Ni-Sliquid slightly decreases with increasing temperature.
This tendency is consistent with the temperature trend measured at ambient pressure(Kucharski et al. 1994).

Application of Synchrotron X-ray radiation to Earthand Planetary Sciences
1. X-ray diffraction and spectroscopic studies under theconditions of the center of the Earth, i.e., 5000-6000 K at 365
GPa
2. Some volatile components such as H2, H2O, CH3, and NH4
are also important materials relevant to the internal
structures of the objects in the outer solar system.
3. Structures and physical properties of silicate liquids(magmas) and metallic liquids (outer core) at high pressure:liquid miscibility, equation of state, viscosity, and interfacial
energy of the liquids.
4. Studies on fracturing and rheological properties of geomaterials. Development of imaging techniques such as X-ray
radiography and tomography under the deformed andstressed conditions. The imaging and tomography are also
applied in volcanology

Fracturing of Earth Materials
Seismicity in Subducting Plates
Rayleigh and Paterson (1965)

Dehydration enbrittlement:

Rheology of Earth Materials:
Disloctions and defects
Mantle convenction andMountain building

Dehydration of hydrous minerals in
subducting platesHT type： 20GPa, >1100 oC

CPO of Akimotoite（Ilmenite MgSiO3)
Shiraishi, Ohtani, Kanagawa,
Shimojuku, Zhao, Nature, 2008

Alumina
PistonT.C.

SampleAkimotoite

Deformation cell
LT type: 20 GPa, <1100oC

Low T
type

Tonga Subduction HT type

MAX-III for Deformation Cubic Anvil Press (D-CAP)
APS: D-DIA 250 ton press: Deformation
experiments to 19 GPa
PF: D-CAP 700 ton press: >20 GPa TZ and LM
Multianvilpress
CCD
cameraX-ray CCD
cameraX-ray intensifier

D-CAP（Deformation cubicanvil press)

SUMMRY
1. X-ray diffraction and spectroscopic studies under theconditions of the center of the Earth, i.e., High temperature at365 GPa: DAC is a useful tool
2. Some volatile components such as H2, H2O, CH3, and NH4
are also important materials relevant to the internal
structures of the objects in the outer solar system: DAC
3. Structures and physical properties of silicate liquids(magmas) and metallic liquids (outer core) at high pressure:liquid miscibility, equation of state, viscosity, and interfacial
energy of the liquids: A large volume press is a useful tool
4. Studies on fracturing and rheological properties of geomaterials. Development of imaging techniques such as X-ray
radiography and tomography under the deformed andstressed conditions. The imaging and tomography are also
applied in volcanology : D-CAP (D-DIA) is useful.

X-ray tomography image(A)

Fe solid?

Cross section(B)fluctuation during heating

Cross section

Fig. 7. 3D image of iron alloy droplets. (A) Fe78S22 droplets quenched from2 GPa 1273 K which has a internal structure exsolved during quenching.(B) A molten droplet with a composition Fe60S40 at 1.8 GPa and 1473 K.

Experimental Method
X-ray tomography experiments were carried out at13BMD beamline, Advanced Photon Source (APS)
using the tomography apparatus driven by 250 t
uniaxial press [Wang et al. 2005]. Monochromatic Xray radiographic images of the entire sample werecollected from all directions by rotating the highpressure tomography apparatus with a step of 0.5o
along the vertical axis, perpendicular to the incident
beam (Fig.5). Used energy of mono-X-ray was 40
keV. X-ray tomography experiments were performedat the pressure of 0.95 GPa and the temperatures upto 1293 K.

High pressure was generated by a toroidal type
opposed anvil apparatus and the cell assembly usedis shown in Fig.6. A large sample volume is requiredfor determination of interfacial tension using thesessile drop method since gravitational force affects
the droplet shape. Toroidal grooves concentrical tothe cylindrical anvil axis provide effective support for
the gasket from large extrusion. As a result, anvils
with toroidal grooves maintain wider anvil gaps thanthose without grooves.

Toroidal anvil

beforecompression

aftercompression

Fig. 6 Toroidal anvil and cell assembly
Fig. 5 High pressure tomography set-up at 13BMD, APS
Experimental conditions
Pressure: 0.95 GPa (40ton)
Cell assembly
Exposure time for imaging: 3 sec.
Sample: Ni70S30 pellet
Image analysis
Capsule: hBN
Image reconstruction:
Gasket: Composite plastic gasket
Tomo_display
3D image viewer: Blob3D[PK450(inner)+UL1000(Outer)]Fig. 7 Toroidal cell assembly