Introduction to PIXE AnalysisCyclotron Research Center, Iwate Medical University, Japan

Koichiro Sera

Catchphrases of our PIXE

1. We’ll give you the results of analyses in the evening, if you take them to our laboratory in the morning.

2. We perform quantitative analysis of any kind of samples.

Inner-shell Ionization and X-ray Detection

electron transition

Production and Detection of K-x rays

K-x ray

Si(Li) Detector

Incident ProtonN-shell

K-shell

M-shell

L-shell

Nucleus

CoulombInteraction

n

Atom in the Sample

from accelerator

Electron ejection

Inner-shell Ionization

PIXE Ion (Proton)EPMA ElectronX-ray Fluorescence Analysis

X-ray

PIXE Ion (Proton)

Particle Induced X-ray Emission Analysis

1

10

100

1000

10000

100000

1000000

20 60 100 140 180 220 260 300 340 380 420 460 500

Channel Number

Coun

ts/Ch

anne

l Fe-Kα e

scap

eTi

-Kα

Ti-Kβ

Fe-Kβ

esca

pe

Mn-

Kα

Cr-Kα

Cr-Kβ

Fe-Kα

Fe-KβSi

-K

Al-K

S-Kα

Cl-Kα

Ga-

Kα

Ca-

Kα

K-Kα

K-Kβ

Ca-

Kβ

Zn-Kα

Ni-Kβ

Ni-Kα

Cu-

Kα

Cu-

Kβ

Pb-Lα

Zn-Kβ

Aerosol

An example of the method of quantification

Ｘi = Ｙi σ ×Ａs × eff s sx

Ｙs σ ×Ａi × eff i ix

Quantitative analysis by the internal standard method

Ｘs × ×Number of atom

Number of atom of the standard element

Ratio of peak yields Ratios of three physical quantities

1. Internal-standard method

(for the samples easy to be homogenized)

Internal-standard method

Weight Measurement of the sample and the internal standard

Addition of the internal standard and homogenization

Drying

Measurement

Beam

Target

4μm Mylar film

Si (Li)

X-ray

Analytical Attributes of PIXE

1 Simultaneous analysis of all elements (Na≦) in a short time(3-10min).

2 High- and almost equal- sensitivity for all elements.

3 Quantitative analysis of extremely small amount of samples(≦1mg).

4 Quantitative and non-destructive analysis of untreated samples. (Hair, Urine, Nail, Blood, Organ etc.)

5 Analysis of liquid samples like an oil, bio-samples staying in alive, large samples such as an ancient pottery, powdered samples such as soil, ash and aerosol etc.

6 Micron-order elemental mapping using a micro-beam (e.g. for a single cell) and beam channeling (e.g. for metals and alloys) etc.

bo ne

proto n beam

bo nex-rays

detector

holder (500 μm M yla r)

hole (20 φ )

a few hairs

proto n beam

hairx-rays

detector

a)

b)

holder (500 μm M yla r)

○Our method doesn’t require any target preparation procedure except for washing before irradiation.

○It is possible to quantitatively analyze as little as one hair of 1 cm in length.

Quantitative analysis of untreated hairs

In-Air non-destructive analysis大気中,非破壊分析

真空内 大気中陽子ビ－ム

考古学試料

生物体試料

生物体試料

フォイル

美術品

Living animals

Living plants

Arts

Archaeological excavations

BeamIn vacuum In air

Ca(Calcium)Fe(Iron)

４８×３９μ

m2

Zn(Zinc)

NoRadiation

6 hours

Micro PIXE camera (MOLT-4)Elemental mapping in a single cell.

Occurrence of Apoptosis

Nation-wide common utilization facility forPET : Positron Nuclear MedicinePIXE : Particle Induced X-ray Emission

since 1995

NMCC

Takizawa Labiratory

Takemi Memorial Hall

Ultra-high field MRI

Nishina Memorial Cyclotron Center (NMCC)

NMCC and Mt. Iwate

Snow scene of NMCC

Small-size Cyclotron at NMCC

Ultra-compact cyclotron developed for PIXE analysisBy Ion Accelerator Co., Ltd.

Cyclotron

The whole system for PIXE analysis

Frequency of PIXE experiments by each research field

0 5000 10000 15000 20000 25000 30000 35000 40000 45000

1

2

3

Fiel

ds

Frequncy of PIXE experiments

ClinicalMedicine

FundamentallMedicine

Public health & hygiene Medicine

EnvironmentalScience

Pharmacology Biolology

Veterinary Medicine

Sitiology

Dentistry

Agriculture

MineralogyArchaeology

Chemistry

GeologyWood

ChemistryMaterialTechnology

TargetPreparation

Measurement

Analysis

Life and Environmental Sciences

Earth Sciences and Others

Development

Integration from1990 to the present time

A THREE-DETECTOR MEASURING SYSTEM USING A PURE-Ge DETECTOR

(for Fluorine analysis)

X-ray collimator

Beam collimator

X-ray absorber

Beam Beam

Acrylitewindow

Faraday cup

Si (Li)Be : 0.025mm

Pure GeBe : 0.025mm25mm2×5mmResolution135eV at 5.9keV460eV at 122keV

Target

Si (Li)Be : 0.008mm

Fluorine is an essential element from the viewpoint of public health and hygiene medicine.

Simultaneous Measuring System of In-Vacuum and In-Air PIXE

Sample (In-Air)

Sample (In-Vacuum)

Si(Li) DetectorsPIXE Room Cyclotron VaultGe Detector

４-Detector 2-Sample Simultaneous Measuring System

Si(Li) Detector

Weight measurement of the sample

Adding an internal standard and nitric acid

Heating in an electric range

Dropping and drying

In 1,000ppm

HNO3

Chemical-Ashing Method Using an Electric Range

External-standard methodfor uniform and dotted sample

Dotted aerosol collected with an impactor etc.

Beam distribution

Sample distribution on the target

External standard

Uniform-beam method

Uniform-sample method

Uniform aerosol collected with a sampler etc.

Uniform and dotted aerosol samples

Example of Target Preparation for Uniform Aerosol Samples(collected with a step sampler)

beam

beam

Example of Target Preparation for Doted Aerosol Samples(collected with an impactor)

beamSample

Doted sample collected with an impactor

Measurement of aerosol samples

beam

Spectrum analysis using SAPIX code (Sera:1989)

Changes of elemental concentration in aerosol samples successively collected in a suburban dwelling in Akita city.

96年6月17日12時～18日11時

1

10

100

1000

10000

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Sampling hour

Con

cent

ratio

n in

ng/

cm3

MgAlSiSCaFeZnNaTiVCrMnNiCuRbPb

1996 June 17 12:00－ 18 12：00

Zn

Powdered Internal-Standard method(for soil, ash, sediment, deposit, tailings, smashed rock etc.)

Weight measurements of a sample and palladium-carbon Mixing (Powdered as they

are)

Sample Palladium-carbon

Standard-free method for Biomedical and Environmental Samples

Standard-free Method of Quantitative Analysis for Bio-Samples.K. Sera, S. Futatsugawa, K. Matsuda and Y. MiuraInt’l Journal of PIXE Vol. 6-3,4 1996 (467-481)

Quantitative Analysis of Bio-Medical Samples of Very Small Quantities by the Standard-Free Method. K. Sera, S. Futatsugawa, S. Hatakeyama, Y. Saitoh and K. MatsudaInt’l Journal of PIXE Vol. 7-3,4 1997 (157-169)

Quantitative Analysis of Powdered Bio-Medical Samples by the Standard-Free Method.K. Sera and S. FutatsugawaInt’l Journal of PIXE Vol. 8-1 1998 (19-32)

Quantitative Analysis of Untreated Bio-Samples. K. Sera, S. Futatsugawa and K. MatsudaNuclear Instr, and Meth, in Phys, Res. B150 1999 (226-233)

Standard-free Method（Quantitative Analysis without Standard)

1

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100

1000

10000

100000

0 50 100 150 200 250 300 350 400 450 500

Channel Number

Cou

nts/

Cha

nnel

Raw spectrumRawspectrum

4 m ppp+コロジオン

1

10

100

1000

10000

0 100 200 300 400 500 600

2.6-15.2keV 領域の連続Ｘ線

Continuous X-rays

+ Collosion

bone

proton beam

bonex-rays

detector

holder (500μm Mylar)

hole (20φ )

a few hairs

proton beam

hairx-rays

detector

a)

b)

holder (500μm Mylar)[1] Standard-free Method of Quantitative Analysis for Bio-samples.

K.Sera, S.Futatsugawa, K.Matsuda and Y.Miura. International Journal of PIXE, Vol.6, No.3,4(1996) 467-481

[2] Quantitative Analysis of Untreated Bio-samples.K.Sera, S.Futatsugawa and K.Matsuda Nuclear Instruments and Methods in Physics Research, B 150 (1999) 226-233

○Our method doesn’t require any target preparation procedure except for washing before irradiation.

○It is possible to quantitatively analyze as little as one hair of 1 cm in length.

Quantitative analysis of untreated hairs

Elemental concentration in hairs reflects that in a human body.

Standard-free Method for Untreated Nails

1

10

100

1000

10000

100000

50 100 150 200 250 300 350 400 450 500

Channel Number

Cou

nts/C

hann

el

K-K

α

Se-K

α

Ca-

Kα

Ca-

Kβ

Ni-K

α

Zn-K

β

Cu-

Kα

Fe-K

α

Fe-K

β

Hg-

Lα

Zn-K

α

Br-K

α

Br-K

β

Pb-L

α

Pb-L

β

Detector No.1Ep = 2.9 MeVwith a 300 μm Mylar

TapeNail

Beam spotTarget holder

Application of a Standard-free Method to Quantitative Analysis of Urine Samples

K. SERA, Y. MIURA and S. FUTATSUGAWA

Human Urine Net Spectrum

1

10

100

1000

10000

100000

50 100 150 200 250 300 350 400 450 500

Channel Number

Cou

nts/

Cha

nnel

K-K

K-K

Ca-K

Ca-K

Ti-K

i-K

Cr-K

As-

K

Fe-K

Br-K

Fe-K

Cu-K

Cu-K Zn

-K

Br-K

RbK

Sr-K

Rb-K

Int'l Journal of PIXE Vol.11-3,4 149-158 (2001)

Target is prepared only by dropping 5μl of urine onto a backing film.

As

The standard-free method for sweat samples

K-K

αC

a-Kα

Ca-

Kβ

Ti-K

α

Mn-

Kα Fe

-Kα

Fe-K

βN

i-Kα

Ni-K

β Br-

Kα

Br-

KβC

u-Kα

Zn-

Kα

Ep=2.9MeV

With a 500μm Mylar

Zn-

Kβ

Pb-Lα

Rb-

Kβ

The total yield of continuous x-rays between 4.4 and 6 keV is used for determining the conversion coefficient for the standard-free method.

Standard-free method for saliva samples

K-K

αC

a-Kα

Ca-

Kβ

Ti-K

α

Mn-

Kα Fe

-Kα

Fe-K

β

Br-

Kα

Br-

Kβ

Cu-

Kα

Zn-

Kα

Ep=2.9MeV

With a 300μm Mylar

Zn-

Kβ

Pb-Lα

Rb-

Kβ

X-ray spectra of tear samples taken from a 26 years-old woman

a) Si(Li) No.1with a 500 μm Mylar absorber

b) Si(Li) No.2without absorber

The effect of specially designed absorber(for geological and mineralogical samples)

with a 300μm Mylar

Method of determining transmission curvesDetermination of Physical Quantities for PIXE by Means of PIXE 1. Absorption CurveSera, K., Futatsugawa, S., Hatakeyama, S. and Saitou, Y.Int'l Journal of PIXE Vol. 4-2, 3, 165-179 (1994)

Tumor: 1 week after transplantation Before injection of Tumor: 1 week after transplantation Before injection of CisplatinCisplatin

Tumor reduced: after injection Tumor reduced: after injection of of CisplatinCisplatin

VX2+E7820

Tumor

3D reconstruction images in tongue

cancer

ClCl-- NH3 NH3 PtPt

ClCl-- NH3NH3

CDDP(CisplatinCDDP(Cisplatin))

Examination of lymphatic vessels as a drug delivery routeA. Fujimura a, K. Sera b , S. Futatsugawa c and Y. Nozaka a

Peripheral injection of CDDP around the tumor

ExplantationExplantation of VX2 of VX2 cancer cellscancer cells

Growing and metastasisGrowing and metastasis Injection of Injection of CisplatinCisplatin Diffusion and movement Diffusion and movement of of Cisplatin Cisplatin

①

②

③

④

IntraIntra--venous injection venous injection 4mg/kg4mg/kg

PeriPeri--tumor tumor injection 0.1mg/ml, injection 0.1mg/ml,

100100μμl = l = 1010μμg/2.5kgg/2.5kg

44μμg/gg/g

100100μμg/gg/g

44μμg/gg/g

22μμg/gg/g

44μμg/gg/g

0.0040.004μμg/gg/g

Whole body

Tongue Deep cervical lymph node

X 1/100

X 1/2X 25

0

1

2

3

4

5

6

R-SML L-SML R-DC L-DC

1mg/ml

0.1mg/ml

0.01mg/ml

Result & Discussion

Effect of Mineral-Rich Water Spraying

←spraying no spraying→

←spraying no spraying→

Soybeans

User friendly common utilization at NMCC

We’ll give you the results of analyses of your sample in the evening, if you take them to our laboratory in the morning.

Thank you for your attention

Sera ：ksera@iwate-med.ac.jp

•NMCC

Ion Accelerator Co.,Ltd

Tohoku Univ.

RIKEN

Tokyo Technology Univ.Tokyo Univ.Tokyo TMITRIHosei Univ.Waseda Univ.Tishiba Co., Ltd.

NIRSTchiba Univ.

Nagoya Univ.Toyota Co., Ltd

Ion technology Center Co., Ltd

Kyoto Univ. Shimadzu Corporation)

若狭湾エネルギー研究センター

ONRIOsaka Univ.

Sumitomo Heavy industry Co., Ltd

Hiroshima Univ.

Kobe steel Vo., Ltd.Kobe Merchant Ship Univ.

Hakodate

Tsukuba

Takizawa

Toukai

Seandai

Takasaki

ChibaTokyoNagoyaKobe

Toya

WakoTsuruga

Kyoto

OsakaHiroshima

PIXE laboratories in Japan

TokyoUniv.

TIARA

Tsukuba Univ.AIST