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X-ray fluorescence analysis
Tokyo University of ScienceDepartment of Applied Chemistry
Izumi NAKAI
反跳電子
散乱 X 線弾性散乱 (コンプトン非弾性散乱 (トムソン
透過 X 線 (吸収)
蛍光 X 線
光電子,オージェ電子
熱
入射 X 線
物
質
Interaction of X-ray with matter
トムソン
コンプトン
X-ray
Heat
PhotoelectronAuger electron
Fluorescent X-ray
Transmitted X-ray(Absorption)
Scattered electron
Scattered X-rayThomsonCompton
sample
(AES)
(XRD)
TransmittedX-ray
(XPS)
(XRF)
Interaction of X-ray with matter and X-ray analysis
sample
Photoelectron
Auger electron
Comptonscattering
Thomsonscattering
FluorescentX-ray
(XAFS)
Absorption
Scattering
Photoelectroneffect
E=hc/λ = 12.398/λ [keV],
λ = long
Energy = low
Wavelength λ
Relationship between λ and E
ex. 1Å= 12.398keV
Particle :energy E [keV]
Wave : wavelength λ[Å]
λ = short
Energy = high
光電子
入射 X 線(E)
蛍光 X 線(ΔE) (Kα線)
Kβ
Lα
Lβ
Mα EbK
EbK < E
原子核
空孔
電子
Kα1
N
ML
K
Kα2
Bohr model and emission of X-ray fluorescence
X-ray energy E > Binding energy Eb
photoelectron
Fluorescence X-ray Kα
X-ray energy E
core
electron
vacancy
Principle of X-ray fluorescence (XRF) analysis
Energy ΔE characteristic to each elementQualitative analysis
Quantitative analysis
Intensity number of X-ray photons → concentration
0
500
1000
0 20 40 60 80X-ray energy (keV)
Inte
nsity
(Cou
nts/
1000
sec)
Ca
Bi
Pb Kα1,2
ReKβ
W Kβ
Ta Kβ
Hf Kβ
Re Kα, Lu Kβ
W
Lu
Yb
Er
Ta
Tm
Hf
Ho
Gd
Dy
Tb
Sm
LaNd Eu
CePr
Ba
Cs
Cd
SnIn
Ag
Sb
Te
U Lβ, Mo KαNb Kβ
Nb Kα
Y KαZr KαTh Lβ
Pb Lα Pb LβBi Lα
Th Lα
U LαSr Kα
XRF spectrum of NIST SRM612 glass
XRF analysis
(a) Wavelength dispersive spectroscopy
(b) EDS Energy dispersive spectroscopy
(a) WDS
(b) EDS
試料
(a) (b)
面間隔 d
分光結晶
試料試料
(a) (b)
面間隔 d
分光結晶Analyzing crystald-spacing
©http://www.postech.ac.kr/dept/mse/axal/index.html
Bragg condition nλ=2dsinθ
Principle of analyzing crystal
©http://www.postech.ac.kr/dept/mse/axal/index.html
Principle of Si(Li) detector → a reverse-biased silicon diode.
Si(Li) detector electron-hole pair 3.85eVex. Fe Kα 6.400keV 6400/3.85=1662 pairs
Bias voltage(-500V) cause current flow. The charge collected at the anode is converted to a voltage by an amplifier. This results in a voltage pulse that is proportional to the number of pairs created and thus to the incident X-ray energy. The resolution is determined by the energy required to create an electron-hole pair (3.8 eV).
X-ray
Be window
Pre Amp.
Slides made by Prof. A. Iida (PF)
©A.Iida(PF)
Characteristics of SR-XRF( X-ray fluorescence analysis)
©A.Iida(PF)
©A.Iida(PF)
©A.Iida(PF)
(1)High Brilliance Source
©A.Iida(PF)
©A.Iida(PF)
©K. Sakurai(NIMS)
©K. Sakurai(NIMS)
©K.Sakurai(NIMS)
(a) Crytal monochormator
World record of MDL by total reflection SR-XRF
(b)XRF spectrum of 0.1ml Ni(1ng/g)solution (20s/point)
C: Ge(220)Johansson type
D:YAP:Ce scintillation counter
3.1x10-16g= 0.31fg3.1ppt(pg/g) 3x106atom
6000 6500 7000 7500101
102
103
104
105
106
100
101
102
103
104
105
Mn Fe Co Ni Nd Gd Sm Tbapple 54 83 0.09 0.91 17 3 3 0.4tomato 246 83 0.09 0.91 - 0.17 3 0.4
NIST 1573a Tomato Leaves (left axis) NIST 1515 Apple Leaves (right axis)
CoK
β 1
NiK
α 1
NiK
α 2
GdL
β 2
FeK
β 1
CoK
α 1
GdL
β 1
NdL
γ 1
MnK
β 1Fe
Kα 1
FeK
α 2
SmLβ
1
NdL
β 2
GdL
α 1
MnK
α 1
MnK
α 2
X-R
ay In
tens
ity [c
ount
s]
Energy [eV]
μg/gmg/kg
MDL(Mn)39.7ppb
MDL(Mn) 0.22ppm
MDL(Fe) 31.5ppb
MDL(Fe) 0.48 ppm
MDL(Co) 3.27ppb
MDL(Ni) 38.4ppb
MDL(Co) 2.51ppb
MDL(Ni) 4.64ppb
Typical XRF Spectra Obtained by R=100 SpectrometerTypical XRF Spectra Obtained by R=100 SpectrometerTrace Metals in Apple and Tomato Leaves (NIST1573a and 1515)Trace Metals in Apple and Tomato Leaves (NIST1573a and 1515)
1sec/point
©K. Sakurai(NIMS)
(2)parallel beam with small divergence
©A.Iida(PF)
©A.Iida(PF)
©A.Iida(PF)
©Y.Suzuki(2002)
Beam profile at focal points made by FZP at 8keV
Spring-8
Application of SR-XRF to in vivo analysis of biological sample
Study of hyperaccumulator plants of As and Cd
Cd isolation
-Cd
Cd
CdCd
Cd
Cd
Cd
Cd
Cd
Cd
Contaminated soil
Cd. ...
.. ...
Phytoremediation
plant remediate
Green technology by plantMerit:no damage,low cost
preservation of surfaceetc…
Element conc./ ppm plantAs 22,630 Pteris vittata L. (モエジマシダ)Cd 11,000 Athyrium yokoscense ( ヘビノネゴザ)Pb 34,500 Brassica juncea (カラシナ)*1 L. Q. Ma, et al., Nature, (2001) , 409, 579.
*1
Some specific kinds of plants are known to be heavy metal hyperaccumulator
ash
Phytoremediation is a technology that uses plants to remove, destroy, or sequester hazardous substances from the environment.
Phytoremediation
As
Arsenic Hyperaccumulator Pteris vitteta L.
(モエジマシダ)
Environmentally friendly low cost technique
Key:Use of hyperaccumulator plantCd
Cd Hyperaccumulator Arabidopsis halleri ssp.gemmifera(ハクサンハタザオ)
HM1: absorption of heavy metal
HM HM
HMHM
HM3: accumulation
HMHM
HMHM
2: transportation
Hyperaccumulation
HMHM
HM
HMHM
Application of SR X-ray analyses
・Two dimensional multi-elementnondestructive analysis in cell level→ μ-XRF imaging
・ in vivo chemical state analysis of metals in the plant
→ X-ray absorption fine structure (XAFS) analysis
・chemical state analysis in cell level→ μ-XANES
As hyperaccumulatorChinese brake fern (Pteris vittata L.)
(As: ca. 22,000 μg /g dry weight)
Arsenic distribution and speciation in an arsenic hyperaccumulator fern by X-ray spectrometry utilizing a synchrotron radiation sourceA. Hokura, R. Onuma, Y. Terada, N. Kitajima, T. Abe, H. Saito, S. Yoshida
and I. NakaiJournal of Analytical Atomic Spectrometry, 21, 321-328 (2006)
pinna
midrib of a frond5cm
Life of fern
spore
prothalliumsporophyte
fertilized
200 μm
30 μm
Pteris vittata L.
Fertile pinnafrond
Cultivation of fern
arsenic-contaminated soil
culture medium containing As(1 ppm 4days)
As level*
pinna:2800 - 4500 µg g-1drymidrib of a frond:84 - 250 µg /g dry
As level in soil:481 µg g-1dry
Term: ~3 weeks
Average As level :~720 µg /gdry
* Anal. By AAS
vertical slicer (Model HS-1, JASCO Co.)
200μm thick
Mylar film Plastic plate
X-ray
moist unwoven paper
Sample preparation for microbeam analysis
freeze dry of frozen
SPring-8 BL37XU
detecor
Sample on XYstageX-ray
K-Bmirror
XY slit (0.2 x 0.2 mm)Si 111 Monochromator
XY slit (0.15 x 0.15 mm)K-B mirror
Sample53 m
In-vacuum undulator
X-ray energyAs: 12.8keVCd: 37.0keV
μ-XRF, μ-XANES
Beam siz: ca. 1 μm
- BEAMLINE DESCRIPTION -The light source : In-vacuum type undulator
(Period length : 32 mm, the number of period : 140)Monochromator : Double-crystal monochromator
located 43 m from the source
fused quartzplatinum coated
250 mm100 mm0.8 mrad
12.8 keV37 keV[1]
fused quartzplatinum coated
100 mm 50 mm2.8 mrad
MaterialSurfaceFocal length (1st mirror)
(2nd mirror)Average glancing angle
Table Details of focusing optics by K-B mirror
- BEAMLINE DESCRIPTION -The light source : In-vacuum type undulator
(Period length : 32 mm, the number of period : 140)Monochromator : Double-crystal monochromator
located 43 m from the source
fused quartzplatinum coated
250 mm100 mm0.8 mrad
12.8 keV37 keV[1]
fused quartzplatinum coated
100 mm 50 mm2.8 mrad
MaterialSurfaceFocal length (1st mirror)
(2nd mirror)Average glancing angle
fused quartzplatinum coated
250 mm100 mm0.8 mrad
12.8 keV37 keV[1]
fused quartzplatinum coated
100 mm 50 mm2.8 mrad
MaterialSurfaceFocal length (1st mirror)
(2nd mirror)Average glancing angle
Table Details of focusing optics by K-B mirror
Instrument ~Spring-8 BL37XU~
SDDSample
Acrylic plate (1 mm thick)
X-ray
検出器
KEK PF BL12CAs K-edge (11.863 keV)Si(111) double crystalFluorescence mode19elements-SSD
in vivo XAFSX-ray
SSD
XAFS analysis
A section of pinna
KAs
frond
X-ray Energy : 14.999 keVBeam size : 50 μm×50 μmStep number : 35 point×90 pointmeasurement time : 1 sec/point
spore
200μm
high
low
X-ray Energy : 12.8 keVBeam size : 1.5 μm ×1.5 μmExposure time : 0.2 sec. / pointPoint : 150 point ×150 point
As
11730
0 Ca
372
0K
425
0
Ca
55
0As
5778
0K
475
0
X-ray Energy : 12.8 keVBeam size : 1.5 μm ×1.5 μmExposure time : 0.2 sec. / pointPoint : 150 point ×150 point M-XRF imaging at Spring-8
As level is low at spore
(3)Energy tunability
Chemical state analysisby Fluorescence -XAFS
©A.Iida(PF)
8.20 8.40 8.60 8.80 9.00 9.20
Energy/keV
Abs
orba
nce
= ln
(Io/
I)
( arb
itrar
yXANES EXAFS
Io I
tμt = ln(Io/I)
Eo
sample
XAFS
Ni K-absorption edge Eo=Eb
X-ray absorption spectrum of LiNiO2
XANES: X-ray absorption near edge structureelectronic state, oxidation number
EXAFS: Extended X-ray absorption fine structurelocal structure (atomic distance and coordination No.)
If
μM = ΣμMiwi [2]
μMi: μM of component i
wi:weight% of component i
X-ray absorption by sample
I/Io = exp(-μt) = exp(-μM ρt) [1]
μ:linear absorption coef.(cm-1)μM:mass absorption coef.(cm2/g)ρ:density of sample(g/cm3)
As K-edge XANES analysis
11.85Energy /keV
Frond TopFrond Base
Midrib AMidrib B
petiole
soil H3AsO4(Ⅴ)
As2O3(Ⅲ)
Nor
mal
ized
Inte
nsity
(a.u
.)
As2O3(III)
Nor
mal
ized
Inte
nsity
(a.u
.)
Frond
Root (freeze dried)in vivo XANES of frondFrond Top
Frond Base
Midrib A上
petiole
Midrib B
Energy / keV11.85 11.86 11.87 11.88
Energy / keV11.85 11.86 11.87 11.88
PF BL-12C
①
②③
④
⑤
⑥
KH2AsO4(V)
Root 先端
基部
1 cm
Summary
・We have established μ-XRF imaging technique utilizing SR to monitor time dependent process of arsenic transfer in a leaf tissue of hyperaccumulator fern.
・This study visually revealed for the first time that arsenic transferred from root to marginal part of leaf within 30min after feeding.
・Arsenic accumulated in the region of vascular bundle and transferred to paraphysis prior to sporangium.
Arabidopsis halleriCd and Zn hyper-accumulator
and
Cd in Rice
Micro X-ray fluorescence imaging and micro X-ray absorption spectroscopy of cadmium hyper-accumulating plant, Arabidopsis halleri ssp. gemmifera, using high-energy synchrotron radiation
Journal of Analytical Atomic Spectrometry, 23, 1068-1075 (2008)
N. Fukuda, A. Hokura, N. Kitajima, Y. Terada, H. Saito, T. Abe and I. Nakai.
Arabidpsis halleri ssp. Genmifera (ハクサンハタザオ)
Arabidopsis halleri is known as a Cd and Zn hyper-accumulator, which contained more than 9000 mg/ kg
Cd and Zn.
XRF imaging of a leaf of A. halleri ssp. Gemmifera.
X-ray Energy : 37 keVBeam size : 50 μm× 50 μmMeasurement points : 60 point×100 pointmeasurement time : 1 sec/point
Zn
2063
0
Rb
13
0
Cd
704
0
Sr
38
0
μ-XRF imaging of a trichome taken from a leaf.
Zn
199
0 K
17
0 Sr
19
0Cd
101
0 Ca
60
0
X-ray Energy : 37 keVBeam size : 3 μm× 3 μmMeasurement points : 59 point×226 pointmeasurement time : 0.5 s/ point
100 μm
Trichomes are epidermal hairs present at the surface of leaves of A. halleri, and their functions are thought to be an exudation of various molecules.
Nano-beam focusing system at SPring-8
(left)Hig precision K-B mirror
(right) Optical parameters of elliptical mirror
Prospect of microbeam analysis
Microbeam → Nanobeam
Yamauchi et al.(Osaka Univ.)
-20
0
20
40
60
80
100
120
-300 -200 -100 0 100 200 300
位置(nm)
強度
(任
意ス
ケー
ル)
理想プロファイル
計測
(a)vertical (b)horizontal
48nm
-20
0
20
40
60
80
100
120
-300 -200 -100 0 100 200 300
位置 (nm)
強度
(任意
スケ
ール
)
理想プロファイル
計測
36nm
Beam profile
Photon Factory BL-12C
High S/N
S-polarization
Si(111)
Total reflection
Θc < 0.3°
19element SSD
sample
19el-SSD
SR-X-ray
XRFX-ray
Nanosheet Monolayer
TXRF-XAFS
Nanosheet(1-layer)
heat
Ti
Ti
0.45 nm
Ti O
Atomic arrangement
transition How to construct the three dimensional structure
Ti1-δO24δ-
Titania nanosheet
Layer structure
Cs0.7Ti1.825□0.175O4
Heating behavior of titania nanosheet by TXRF-XAFS
Material Science
Ti K-edge XANES spectra as a function of temperature
Anatase
As grown
600℃
700℃
800℃
900℃
nanosheet
nanosheet
Nanoーsheet
4950 4970 4990 5010Energy / eV
Norm
aliz
ed inte
nsit
y
Anatase
As grown
600℃
700℃
800℃
900℃
(Reference)
©Fukuda&Nakai
Bulk crystal: stable phase
800℃ → rutile
400℃ → anatase
AnataseNanocrsytal
(4)High energy X-ray
High energy SR-XRF
Bi Kα 76.35 Eb=90.57 U Kα 97.17 Eb=115.66keV
Fig.
P Ca MnZn Br
Zr RhSn
CsNd
TbYb
ReHg
At
U
Zr Rh Sn Cs Nd Tb YbRe Hg At U
0
20
40
60
80
100
120
0 10 20 30 40 50 60 70 80 90 100
Atomic Number
Ener
gy
(KeV
)Kα1
Kβ1
Lα1
Lβ1
X-ray fluorescence energies of K & L lines v.s. atomic number
Z (Atomic Number)
Ener
gy/k
eV
0
2000
4000
0 5 10 15 20
Energy/keV
Intens
ity
Problem of conventional XRF analysisoverlapping of heavy elements L lines as light elements K lines
Sample porcelain , Source:Mo Ka X-ray 40 kV-40 mA , time:1000sec
Rb Kβ,Y Kα
Sr KαRb Kα
Cu Kα
Ni Kα Pb Lα
Ca Kα
Mn Kα
Ti Kα
K Kα
Fe Kα
Fe Kβ
SnSb
La NdDy
TmBiLu
Energy of heavy element L lines XRF peak
Si(400)MonochromatorSR
slit
GeSSD
I.C.
XYステージ
sample
Eliptical multipole wiggler (Gap:160~25.5 mm)Excitation energy:116 keV (100-150 keV)Beam size:1~0.1 mm2
PC
BL08W (for High-energy inelastic scattering experiments)
Experimental setup for high energy XRF
MCA
0
500
1000
0 10 20 30 40 50 60 70 80X-ray energy (keV)
Inte
nsity
(Cou
nts/
1000
sec)
W
Lu
YbEr
Ta
TmHo
Hf
Gd
Bi
Dy W KβSm
La
Nd
Eu Tb
Pb*
Ta Kβ
Hf Kβ
Lu KβCe
Pr
Ba
Cs
XRF spectrum of NIST SRM612 glass: 61 trace elements in 50ppm level(*scattering)
Rb
Nb
CdPb
Ca
Sn
Mo
In
Ag Sb
Te
0
500
1000
1500
0 10 20 30 40 50 60
X-ray energy / keV
Inte
nsity
/ co
unts
W Kα1,2
Hf K1,Yb Kα1,2
Dy Kα1,2Er Kα1,2
Ba Kα Ba Kβ
Nd Kα
Nd Kβ
Sm Kα
Ce Kβ
Gd Kα
Ce Kα1,2
La Kα
Cs Kα
Fe Kα
Fe Kβ
Mn Kα
Pb Lα,βSr Kα
Nb Kα
Ba esc.
Rb Kα,βZr Kα,β
XRF spectrum of JG1 excited at 116keV for 1000sec.
Contents/ ppm Ipeak Iback MDL/ppmFe 2.02a) 1557 366 0.097a)
Rb 181 577 281 30.8Sr 184 719 258 19.2Zrb) 108 395 293.5 54.7Cs 10.2 280 181 4.2Ba 462 7205 354.5 3.8La 23 535 355.5 7.2Ce 46.6 520 86 3.0Nd 20 862 154.5 1.1Sm 5.1 136 45 1.1Gd 3.7 108 42.5 1.1Dy 4.6 110 41 1.3Er 1.7 86 51.5 1.1Yb 2.7 125 61 1.0Hf 3.5 268 98.5 0.6W 1.7 737 199.5 0.1
MDL for JG1 sample
0.001
0.01
0.1
1
10
0.01 0.1 1 10
Metal concentration (ng)
Nor
mar
ized
net i
nten
sity
(I Lu/I
Gd)
Lu
Calibration curves for Lu using K-lines XRF spectra
. Application field of high energy XRF
・Archaeology for nondestructive provenance analysis
・Forensic analysis
・Industrial chemical analysis of high-Tech materials
・ Geochemistry
Principle of Provenance Analysis of Cultural Heritages
Raw material → Porcelain Stone
Trace element composition tells the locality
Role of Heavy Elements
• Cosmic abundances of the heavy elements with atomic number larger than 26 (Fe) are small compared with the lighter elements.
• They exhibit characteristic distribution in earth, for the heavy elements such as rare earth and U often posseslarge ionic radii and high oxidation states.
• The trace elements often substitute for major elements, whose manner is largely affected by the nature of the elements such as the ionic radii, oxidation state as well as the PTC condition.
Good fingerprint elements
→ High energy SR-XRF analysis
・肥前(Arita) a加賀(Kutani)
・福山姫谷(Himetani)
・有田
・伊万里、嬉野
・波佐見
Colored Porcelain Since 17th Century 17Cの色絵の磁器
Provenance analysis of Old-Kutani China wares
based on the information of their material history
obtained by high energy XRF
Kutani china wares were first produced in the late 17th century in the Kaga Province in Japan. In 1710, however, after half a century of continuous production, the kiln was suddenly closed. Pottery from this early period is known as Old Kutani, which is extremely precious. However, there is a possibility that the Old Kutani might come from Arita, another famous production place of porcelain since 17th century in Japan. Therefore, identification of Old Kutani and Arita is an important and mysterious problem in Japanese art history. It was expected that high-energy XRF analysis utilizing synchrotron radiation from SPring-8 would reveal the origin of the source materials. This is the first nondestructive analysis of museum grade samples of Old Kutani.
)とうP
Kutani
Himetani
Arita
Raw Material
Porcelain Stone tells the Locality
Samples
◆Fragments of porcelain excavated at each
old kiln of Kaga, Arita, and Fukuyama.
Kutani: 121 Arita: 57 Fukuyama: 10
◆Museum grade samples which are thought
to be original: 6
0
1000
2000
3000
0 10 20 30 40 50 60 70Energy / keV
Inte
nsity
/cou
nts
Fe
PbRb
Y
La
Hf WZr
NdCe
Cs
Er
Gd
Sm
Dy
Yb
Sr
Ba
Se
XRF spectrum of fragments of china ware excavated from Old Kutani kiln
H 0 1H 0 2H 6 0H 6 4H 1 4H 3 3H 5 4H 5 2H 4 1H 5 9H 2 8H 6 3H 2 9K 0 5K H 8H 3 5H A 2K 1 7K 1 8K 3 2K 1 0 3H 4 6H 0 3H 5 7H 3 1H 6 8H 0 7H 5 5H 0 9H 1 6H 2 7H 5 6H 6 8H 2 3H 4 0H 1 5K M 1K 1 2K 1 4H 3 4H 5 1H 6 2H A 5K M 2H 0 4H 6 7H 1 3H 3 2H 6 1H 6 6H 6 5H M 1H M 3H M 5H M 6H M 8H M 9H M 2H M 4H M 7H M 1 0K 0 6K 1 3K 1 9K 2 1K H 5K 2 0K 0 8K 2 6K 2 8K H 1K H 3K 1 5K Y 2K 1 0 5K N 1H 1 0H 3 9H 5 8H 5 3H 3 0H A 6H 1 1H 1 2H A 1H 4 7K 2 7K 1 0 9K 5 2K 4 7K 5 1K 5 6K 6 0K 5 9K H 7H 4 3K 3 4K Y 2K Y 3K 5 3K H 1K 0 7K 0 9K 1 6K 2 3K M 1K 3 7K M 2K 4 9K 2 2K 4 8K 3 3K 5 0K 5 5K 3 9K 2 5K 1 0 1K 2 9K H 3K 3 8K H 5K 3 5K 4 4K H 8K Y 3H A 3
0 5 1 0 1 5 2 0D i s t a n c e
Cluster analysis of fragments of china wares using normalized XRF peak intensities of Ba, Ce, Nd
Kutani
Kutani & Arita
Fukuyama
Arita
Ba/Ce-Nd/Ce plot
0
4
8
12
16
0 0.2 0.4 0.6 0.8 1 1.2Nd/Ce
Ba/
Ce
原明窯小溝上百間窯ダンバギリ窯窯の辻窯猿川窯長吉谷窯下白窯柿右衛門窯鍋島藩窯不動山皿屋谷二号窯吉田二号窯三股古窯永尾本登窯辺後の谷窯三股新登窯福山姫谷窯九谷一号窯九谷二号窯吉田屋窯若杉古窯八間道耳聞山今九谷山代
KutaniKutani
AritaArita
FukuyamaFukuyama
Material History
During the formation and existence of a substance, the information of its material history is recorded in the substance in various forms such as the concentration, distribution, and chemical state of the trace elements as well as chemical composition, structure, isotope ratio of the major elements.
Every substance was produced in the past. The law of causality determines the chemical state of a substance.
A latent record of information stored ina substance recording its origin and history
Big-bang ElementaryParticle
Hydrogen atom
light elements
heavy elements
moleculeminerals
rock star
geological process
life humanbeings
civilization
evolution of life
chemical evolution
Material Evolution:material world is continuous15 billions years ago
nuclear fusion
Stream of Time →
neutron capture & β-decay
Application of the material history: Information of the material history can be
used in various scientific fields
• Archaeology, forensic analysis, geology,geochemisty→To reveal the past based on the material history.
• Biological sciences: life history, migration history, environmental problems
• Industrial application: prediction of source material, production method and patent related problems
• Environmental science: monitoring of environmental change→industrial, biological, and social activities etc.
Highly sensitive nondestructive X-ray analyses utilizing SR are most suitable techniques to reveal the material history of the sample.
Cobalt blue 0.0002% Co
Importance of trace element
S&W Gunshot Residue
SPring-8 BL08W
Characteristic element: Ba,Sb, Pb
Ba
SbPb Pb
High energy SR-XRF characterization of trace gunshot residue
Forensic application
0 20 40 600
500
1000
1500
WTaSnNb
ZnFeTi
coun
ts
Energy(keV)
A
0 20 40 600
500
1000
Nb
Zn
Ba
Ti
Energy(keV)
B
0 5 10 15 200
5000
10000
SiAlFe
Ti
Cou
nts
Energy(keV)0 5 10 15 20
0
5000
10000
Al
TiCo
unts
Energy(keV)
EPMA EPMA
Ninomiya(2004)
High energy XRF characterization of trace heavy elements in white car paints (paints A & B) compared with X-ray microprobe (bottom)
Chemical speciation of arsenicChemical speciation of arsenic--accumulating accumulating mineral in a sedimentary iron deposit by mineral in a sedimentary iron deposit by
synchrotron radiation multiple Xsynchrotron radiation multiple X--ray analytical ray analytical techniquestechniques
S.ENDO,Y.TERADA,Y.KATO,I.NAKAIEnviron.Sci.Technol.2008,42,7152.
Comprehensive characterization of As(V)-bearing iron minerals from the Gunma iron deposit by
Sample the Gunma iron deposit of quaternary age
(5) (5) multiple Xmultiple X--ray analytical techniqueray analytical techniqueμ-XRF imaging, m-XRD,XAFS and SEM
Decompositon of As containing minerals by acidic water
As As fixationfixation
・Precipiationex.) Fe3+ + AsO43- → FeAsO4↓
・Adsorptionα-FeO(OH)
・biological effectbiomineral formation
Remediation of As poisoning
As
Hot spring
BackgroundBackground
3
Natural behavior of arsenic at volcanic region
200 μm
As Fe
SPring-8 BL37XU
X-ray: 12.8 keVBeam size : 1.8 μm×2.8 μmStep size : 2.0 μm×3.0 μmMeas. time : 0.1 s/pointDetector : SDD
SRSR--μμ--XRF XRF XRF imagingXRF imaging
3500
0
15500
0
Purpose: which mineral accumulate arsenic?
strengite FePO4·7H2O ?jarosite KFe3(SO4)2(OH)6 ?goethite FeOOH?
As 20 μm
SRSR--μμ--XRF & SEMXRF & SEM--EDS EDS
Fe SEM image1800
0
11000
0
S (SEM-EDS) P (SEM-EDS) K (SEM-EDS)
Positive correlation between As and P, negative for S and K
Beam size: 1.8 μm×2.8 μmStep size : 1.0 μm×1.0 μm As at the region with peculiar concentric morphology
strengite FePO4·7H2Ojarosite KFe3(SO4)2(OH)6
As 20 μm
SEM-EDS spectrum
SRSR--μμ--XRF & SEMXRF & SEM--EDS EDS
Fe SEM
Energy / keV
Inte
nsity
0 5 10 12
Fe Kα
Fe KβAs Kα
P Kα
As LαIn
tens
ity
Energy / keV
O Kα
1800
0
11000
0
0 2 4 6 8 100 5 10Energy / keV
Inte
nsity
O Kα
S Kα
K Kα
Fe Kα
Fe KβFe Lα
Beam size: 1.8 μm×2.8 μmStep size : 1.0 μm×1.0 μm
Localization of As.
strengite FePO4·7H2Ojarosite KFe3(SO4)2(OH)6
XRDXRD
XRD pattern (P1)
P1
P2
XRD point
X-ray : 12.8 keVBeam size : 50 μm×50 μmMeas.time : 12 min. / sampleIP (Imaging Plate)
* strengite FePO4·7H2O PDF No. 33-667** jarosite KFe3(SO4)2(OH)6 PDF No. 22-827
P1 P2 ストレング石 鉄明礬鉱d / Å I / I0 d / Å I / I0 hkl d / Å I / I0 hkl d / Å I / I0
101 5.93 45003 5.72 25
102 5.09 70
110 3.65 40
201 3.11 75113 3.08 100
202 2.965 15006 2.861 30
204 2.542 30
111 5.509 60
020 4.954 30201 4.383 85211 3.996 45121 3.959 13112 3.719 25
221 3.281 17122 3.114 100
311 3.002 45131 2.949 45
231 2.631 11132 2.546 50
5.49 55
4.95 434.37 1004.00 22
3.27 213.12 53
2.99 162.95 19
2.56 45
5.93 325.75 14
5.10 56
3.63 32
3.11 723.07 100
2.97 122.88 8
2.55 20
P1 P2 ストレング石 鉄明礬鉱d / Å I / I0 d / Å I / I0 hkl d / Å I / I0 hkl d / Å I / I0
101 5.93 45003 5.72 25
102 5.09 70
110 3.65 40
201 3.11 75113 3.08 100
202 2.965 15006 2.861 30
204 2.542 30
111 5.509 60
020 4.954 30201 4.383 85211 3.996 45121 3.959 13112 3.719 25
221 3.281 17122 3.114 100
311 3.002 45131 2.949 45
231 2.631 11132 2.546 50
5.49 55
4.95 434.37 1004.00 22
3.27 213.12 53
2.99 162.95 19
2.56 45
5.93 325.75 14
5.10 56
3.63 32
3.11 723.07 100
2.97 122.88 8
2.55 20
strengite jarosite
11.85 11.9
Nor
mal
ized
inte
nsity
(a.u
.)
11.85 11.86 11.87 11.88 11.89 11.90 Energy / keV
μμ--XANESXANES
P1
P2
XANES points
As exists as As(V) in the sample(AsO43-, HAsO42-)P1
P2
As(V) in strengite
KH2AsO4
KAsO2
As(V)
As
AsO43-
As K-edge XANES spectrameasured by 2μm X-ray beam
strengite (FePO4・2H2O)
動径構造関数
0 1 2 3 4 5 6r / Å
FT M
agni
tude
P1
P2
As(V) instrengite
As-OAs-Fe
μμ--EXAFS EXAFS
EXAFS測定箇所
EXAFS
P1
P2
As(V) in strengite
OFe
O
OFe
1.683.36
1.69
1.683.35
4.04.0
4.0
4.04.0
Atom r / Å CN
P1
P2
As
As
OAsO43- イオン
As→AsO4AsO4 tetrahedra-Fe(III)octahedra
Fe
As
O
k / Å
k3χ(
k)
― Meas.・ fitting
P1
2 7 12
Curve fitting
strengite FePO4·7H2O
Crystal structure of strengite (FePO4・2H2O)
PO4
FeO4(OH)2 Octahedron
O P Fe
AsO4
As
As in strengite
1.68 Å
3.36 Å
As accumulation mechanismAs accumulation mechanism
PO4 → AsO4
As in solution
AsO43-
Substitution of PO4 tetrahedra instrengite (FePO4・2H2O) by AsO4 teterahedra
ConclusionLimitation of the SR-XRF
1.Microbeam analysis
i) the thickness of the sample should be in the order of beam size
→ preparation of thin sample is not easy
ii) it takes long hours to carry out two dimensional mapping
because of large numbers of measurement points
2. Low excitation efficiency for light elements
3. Special efforts is necessary to carry out quantitative analysis
4. Sample damage should be considered if you use brilliant Undulator SR Source or white X-ray radiation. Especially, care must be taken about photo-reduction/oxidation of the component elements.
However!
Attractiveness of SR-XRF1.Nondestructive analysis, multielemental analysis
2. Two dimensional resolution
3. Easy to carry out the analysis and easy to understand the results
4. Basic optical system for EDS analysis is simpleSR → Monochromator → sample → detector
5.We can analyze almost any samples
size → from cell level to sculpture, paintings
in situ、 in vivo、 in air at any temperature
6. Information
concentration: major(%), minor, trace(ppm) elements C ~Na ~ U
distribution: from nm level to cm level
chemical state ( oxidation state, local structure) C ~ Si ~ U
7.Multiple SR-X-ray analysis: combination with X-ray diffraction and XAFS
SR-XRF is waiting for you.
Come and just try it !
Invitation to SR-XRF