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