Die Anwendung der Röntgenstrahlung in den Umwelt- und

Transcription

Die Anwendung der
Röntgenstrahlung in den Umweltund Lebenswissenschaften
Christina Streli
Atominstitut, TU Wien
Strahlenphysik
• Wilhelm Conrad Röntgen
– * 27. März 1845 in Lennep (heute
Stadtteil von Remscheid) im Bergischen
Land (D)
– † 10. Februar 1923 in München
– 8. November 1895 Entdeckung der XStrahlen
– 1901 erster Nobelpreis für Physik; "als
Anerkennung des außerordentlichen
Verdienstes, das er sich durch die
Entdeckung der nach ihm benannten
Strahlen erworben hat".
– die 50.000 Kronen Preisgeld stiftet er
der Universität Würzburg
1
•
Welches Element ist
•
wo
•
in welcher Konzentration
•
In welcher chemischen
Bindung ?
Fundamentals
Energy dispersive X-ray Fluorescence Spectrometry (EDXRS)
Interaction:
• Photoeffect :
Auger effect
X-Ray Fluorescence
• Elastic (coherent) scattering
• Inelastic (incoherent) scattering
X-Ray source
Energy dispersive X-Ray detector
X-ray tube
Synchrotron radiation
sample
2
Fundamentals
Energy dispersive X-ray Fluorescence Analysis (EDXRF)
Echar = EK - EL
Seite 5
EDXRS at the Atominstitut
EDXRS
Standard XRF
Micro XRF
(µ-XRF)
Total Reflection XRF
(TXRF)
Absorption Spectroscopy
in fluorescence mode (XAS)
Disadvantage
• scattering radiation from
sample & sample carrier
 high background
Advantage
• simultaneous qualitative &
quantitative determination of
major, minor and trace
elements (down to ppm level)
Seite 6
3
EDXRS at the Atominstitut
EDXRS
Standard XRF
Micro XRF
µ-XRF
TXRF
Disadvantages
• complex setup and data
evaluation
• time
consuming
measurements
Advantages
• spatially resolved analysis
(10 – 60µm)
• 2D & 3D resolution
Seite 7
EDXRF at the Atominstitut
EDXRF
Standard XRF
Micro XRF
µ-XRF
TXRF
Advantages
• background reduction
• double excitation of sample
EDX detector
Collimator
• small distance sample  detector
(~1mm)  large solid angle
Low detection limits
• low sample mass
required
• angle dependence of fluorescence
signal
 information about type of sample
(bulk, particle, film, implantation)
Seite 8
4
Fundamentals of TXRF

crit
 2  
20.7
 
E
crit [mrad], E [keV],  [gcm-3]
n  1    i
Penetration depth (nm)
17.5 keV in Si
penetration depth (nm)
10000
1000
100

10
crit
1
0
0,5
1
1,5
2
angle(mrad)
2,5
3
3,5
4
LLD in the pg range with tube excitation
Seite 9
EDXRF
Standard XRF
Lab:
• Chem. Analysis
Micro XRF
µ-XRF
Lab:
SR:
••Imaging
2D & 3Dof low
Zimaging
elements
scanning &
tomography
• Phase contrast
imaging, SIT
TXRF
Lab:
SR:
••Chem.
Chem.Analysis
Analysis
••Low
LowZZAnalysis
Analysis
••GI
XRF, Implants
Surface
Analysis
• Surface
(Wafer)Analysis
•(Wafer)
GI-XRF,
Lab:
SR:
no
intenseSpeciation
energy- in
• Chem.
tunable
available
TXRF source
geometry
• Chem. Speciation in
micro XRF mode
depth profiling
Why Synchrotron Radiation?
Seite 10
5
Synchrotron Radiation
Synchrotron radiation is an electromagnetic radiation emitted when charged particles
with relativistic speed undergo radial acceleration.
Seite 11
Synchrotron Radiation
Why Synchrotron Radiation?
• High Intensity
• High collimation vertical to the orbital plane (little angular divergence)
• Continuos energy distribution  monochromators can be used over a wide range of energies
• Photons are highly polarized in the orbital plane  significant background reduction in EDXRF
Detection Limits in the fg range for medium Z Elements
Influence of radiation source upon S and IB:
LLD 
3 IB

S
t
• Intensity (larger S and IB)
• Spectral distribution
(monochromatic excitation  smaller IB)
• Linear polarization (smaller IB)
Seite 12
6
EDXRF
Standard XRF
Micro XRF
µ-XRF
Lab:
• Chem. Analysis
TXRF
Lab:
• Imaging of low
Z elements
SR:
• 2D & 3D
imaging
scanning &
tomography
• Phase contrast
tomography, SIT
Lab:
• Chem. Analysis
• Low Z Analysis
• GI XRF, Implants
• Surface Analysis
(Wafer)
Lab:
no intense energytunable source available
SR:
TXRF geometry
micro XRF mode
SR:
• Chem. Analysis
• Low Z Analysis
• GI XRF, Implants
• Surface Analysis
(Wafer)
Seite 13
X-ray Absorption Spectroscopy
XANES
EXAFS
The x-ray absorption spectrum shows a fine structure if it
is sampled with a high resolution.
absorption involves electronic transitions
fine structure affected by energy and density of
electronic states and transition probabilities
influence of the environment:
neighbouring atoms (EXAFS), bond type (XANES)
EXAFS
XANES
XANES: X-Ray Absorption Near Edge Structure, ends 50-100 eV above the edge
EXAFS: Extended X-Ray Absorption Fine Structure, starts 50 - 100 eV above the edge
Seite 14
7
SR-TXRF @ HASYLAB beamline L
L
Experimental Setup @ HASYLAB beamline L
Detector (SDD)
Cross
Slits
CCD camera
collimator
Beam
stop

DORIS-III
z
reflector
Ta-wedge
Vacuum chamber
Monochromator
Si-111
Multilayer Pair
Si-113
ML  intensity gain of 80-100
only small increase of scatter peak
Seite 15
Speciation of arsenic in xylem of plants
L
Coop: Eötvös Univ. Budapest, Prof. Zaray, Dr. Mihucz
Motivation:
Arsenic is contained in groundwater in Eastern Hungary (up
to 2µmol). Speciation of As in xylem is important to:
• understand how plants metabolise and transform As
Xylem
• assess the health risk caused by As entering the food chain
(different As species have different toxicity; e.g. As(III) and
As(V) )
Experimental:
•At two leaf stage:
transferred in solution with arsenic compounds and
reduced phosphate concentration
Source: www.fairchildgarden.org
• After 30 days from germination (17 d arsenic):
- stem cut 2 mm above root neck
- sap collected with micropipettes
 for 1 hour into PE vials immersed in ice salt bath
Seite 16
8
L
Advantages of XAS in TXRF geometry:
• TXRF offers good sensitivity for XANES speciation of traces (ppb range)
• only small sample volumes are required
• simple sample preparation (just pipetting some µl on reflectors)
 prevents unwanted oxidation of sample during preparation
Seite 17
L
Results:
• Speciation of As was possible down to the 30ppb level
• As(III) in nutrient solutions oxidises easily to As(V)
• Cucumber roots convert As(V) to As(III)
• Best poster award, Denver X-Ray Conference 2006
• F. Meirer et al., Application of synchrotron-radiation-induced TXRF-XANES for arsenic speciation in cucumber
(Cucumis sativus L.) xylem sap, X-Ray Spectrometry 36 (2007) 408-412.
9
TXRF- (& XANES) analysis of aerosols
Coop: Univ. Hamburg, Prof. Broekaert, Dr. Ulla Fittschen
L
Motivation:
To understand the effect of aerosols on global climate a
detailed understanding of sources, transport, fate and
the physical and chemical properties of atmospheric
particles is necessary.
The chemical speciation of the elements is of
relevance for the environmental impact.
Berner impactor 10 stages
16 µm – 0.015 µm
Seite 19
TXRF- (& XANES) analysis of aerosols
L
Advantages of SR-TXRF:
• only small sample mass required
• sampling time can be diminished
 time resolved investigation of atmospheric events
• simple sample preparation
(aerosols directly collected on reflectors)
• TXRF offers good sensitivity for XANES speciation of traces
Seite 20
10
Quantitative results
L
Pb high in
very small
particles <
130 nm!
20 min day time sampling in the city of Hamburg
8: 16 – 8 µm, 2: 8 – 2 µm, 0.13: 2-0.13 µm,
Seite 21
XANES of Fe from various impactor stages
L
Fe K-edge Aerosols
FeSO4
6
16-8µm
6-4µm
4-2µm
2-1µm
4
arb. units
1000-500nm
500-250nm
250-130nm
130-60nm
2
•amounts of Fe on the
collection plates were
very low- around 500900 pg
•Fe was present in the
oxidation state of three
and very likely in form of
Fe(III)oxide in all
impactor stages.
60-30nm
30-15nm
Fe2O3
0
7100
7120
7140
7160
7180
energy (eV)
U. E. A. Fittschen, F. Meirer, C. Streli,P. Wobrauschek, Julian Thiele,G. Falkenberg, G. Pepponi,
Characterization of Atmospheric Aerosols using SR-TXRF and Fe K-edge TXRF-XANES,
Spectrochimica Acta B, 2007
11
Wafer surface analysis with TXRF
Si wafer contamination control is
required by the semiconductor
industry to produce high quality
products with fast decreasing
dimensions and prices. Metallic
contamination
have
negative
effects on gate oxide properties,
resulting
in quantifiable yield
losses.
Limit
of
total
surface
contamination : 5E9 atoms/cm2
Wafer surface analysis is the main application of TXRF worldwide!
Seite 23
Accreditation for wafer surface analysis with TXRF
Mission
The main interest of the Atominstitut is focused on research and
education of students. The “know-how”, as it will be gained during
the accreditation process, as well as the maintenance phase of the
achieved levels is of interest for the TU Wien.
Within the EC project ANNA the Atominstitut has to present several
deliverables. One is to contribute to the milestone “Accredited
reference laboratories named ‘golden lab’ ”: European researchers
and industrial users require comparable results, when analytical
methodologies are supplied by different research installations.
Moreover, industrial partners and suppliers are usually certified.
Therefore the research institutes supplying services and research to
industry are requested to apply for quality accreditation in order to
support the industrial certification. The aim is to establish reference
laboratories inside the ANNA network per analytical technique
families which will be certified according to quality standards.
24
12
Pyramid-like
Document structure
Quality
manual
Process descriptions
Manuals, Standard Operating Procedures
accreditation according to
ISO 17025
25
26
13
Validation: SRM from NIST
NIST 1643e ( trace elements in water)
27
Seite 28
14
Gunshot residue investigation
( Schmauchspur Untersuchung)
Cooperation with
Landeskriminalamt Wien
Aim: investigation of gun shot residue in 3 m distance
Local distribution of gun shot residue
Seite 29
Schussanordnung und Waffenkonfiguration
Makarov (9mm), Munition
MAK Sellier & Bellot (6,2g)
(1997)
Glock 17 (9mm),
Vollmantelmunition Geco (8g)
R1
R2
R3
R4
R5
R6
15
Spektrum der Schmauchspuren der beiden Waffen
Spektrum Vergleich Zoom
Makarov
Glock
50000
Pb-M
45000
40000
2 Pb-L
35000
30000
Counts
Mo-Scatter
25000
Si
20000
Pb-L
15000
Cu
10000
Pb-L
2 Ba
5000
0
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Energie [keV]
„Fingerprint“
Fingerprint
Makarov
Glock
250000
200000
Counts
150000
100000
50000
0
Al-Ka
Cl-Ka
K-Ka
Ca-Ka
Ti-Ka
Cr-Ka
Fe-Ka
Ni-Ka
Cu-Ka
Zn-Ka
Cd-La
Sn-La
Sb-La
Ba-La
Elemente ohne Pb
16
EDXRF
Standard XRF
Lab:
• Chem. Analysis
Micro XRF
µ-XRF
SR:
• 2D & 3D
imaging
scanning &
tomography
• Phase contrast
tomography, SIT
TXRF
Lab:
•SR:
Chem. Analysis
••Low
Z Analysis
Chem.
Analysis
••GI
XRF,
Implants
Low
Z Analysis
••Surface
GI XRF,Analysis
Implants
•(Wafer)
Surface Analysis
(Wafer)
SR:
• Chem. Speciation
in TXRF geometry,
in micro XRF mode
Lab:
• Imaging of
low Z elements
Seite 33
Synchrotron Micro-XRF
Advantages:
• High flux:
up to 10E8 photons/s/µm2 (ESRF)  short measuring times
• Monochromatic &
use of polarisation:  LLD ~10ng/g (ppb) in biological matrix  trace elemental capabilities
• Special setups:
3D capabilities
• Spatial resolution: ~15µm spot size
Seite 34
17
Imaging: Trace elemental distribution in human bone
Cooperations:
• Ludwig Boltzmann Institute of Osteology, UKH Meidling, Austria
• Department of Orthopaedics, Vienna General Hospital, Medical University of Vienna, Austria
• Department of Forensic Medicine, Medical University of Vienna, Austria
• Max-Planck Institute for Colloids and Interfaces, Potsdam, Germany
• IAEA, Seibersdorf Laboratories, XRF Instrumentation Unit, Austria
• ITC-irst, Povo (Trento), Centro per la Ricerca Scientifica e Tecnologica, Italy
• HASYLAB at DESY, Hamburg, Germany
• ANKA, Institut für Synchrotron Strahlung, Karlsruhe, Germany
Seite 35
Motivation for investigation of Pb
What we know:
• Lead (Pb) is toxic and accumulates in the human skeleton  95% of the total body burden
 biological half life ~20a
• Pb is associated with diseases of the skeletal system
it plays a role in osteopenia
inhibits fracture healing
intra articular Pb leads to osteoarthritic changes in the knee joints
What we don‘t know:
• How is Pb distributed in calcified tissue on the microscopic level?
• Difference between subchondral bone & (non) calcifed cartilage ?
What can we do?
• Synchrotron radiation induced micro X-Ray Fluorescence Analysis (SR-µXRF)
What do we get?
• Non-destructive detection of trace elements in biological matrix at the femtogram level
• Spatial resolution in the µm range
• Multielement technique -> simultaneous detection of different chemical elements
Seite 36
18
Bone Histology – Crash Course
Backscattered Electron Image (BE), Patella
Cortical
bone
Trabecular bone
1mm
Seite 37
Bone Histology – Crash Course
Articular cartilage
Calcified cartilage
Subchondral bone
Tidemark
100µm
Seite 38
19
Confocal Micro-XRF 3D imaging
L
ANKA Fluo/Topo:
Multilayer: W/B4C
Energy:
17keV
Detector: Si(Li)
Depth res.: 19µ[email protected]
HASYLAB beamline L:
Multilayer: Ni/C
Energy:
17keV
Detector: Vortex SDD
Depth res.: 22µ[email protected]
RöntgeSeite 39
Confocal µ-XRF
L
sample
inspected
volume
detector
incident beam
For Au La
20µm
22µm
detector
14µm
height
beam
horizontal
sample
plane
incident beam
vertical
sample
plane
beam spot
to detector
20
Results: Control Sample
L
Information only from surface layer!
I….articular cartilage
II…tidemark
III..calcified cartilage
IV..subchondral bone
V…cement line
10
Ca 1.04E+4
Zn 7.1E+2
Sr 3.3E+2
Pb 7.9E+2
9
fluorescence intensity [a.u.]
8
7
6
5
4
3
2
1
0
0
50
100
150
200
250
300
350
displacement [µm]
400
450
500
Seite 41
3D Elemental Distribution
N.Zoeger, P. Roschger, J.G. Hofstaetter, C. Jokubonis, G. Pepponi, G. Falkenberg, P. Fratzl, A. Berzlanovich, W.
Osterode, C. Streli and P. Wobrauschek, Osteoarthritis and Cartilage 14 (9), 906-913 (2006)
N.Zoeger, C.Streli, P.Wobrauschek, C.Jokubonis, G.Pepponi, P.Roschger, J.Hofstaetter, A.Berzlanovich, D.
Wegrzynek, E.Chinea-Cano, R.Simon, G.Falkenberg, X-ray Spectrometry DOI: 10.1002/xrs.998 2007
21
Results
Seite 43
SR-µXRF
Sr in bone
Levels and spatial distribution of trace elements in
trabecular bone following strontium treatment in
calcium deficient rats
B. Pemmer1, F. Meirer1,2, J. G. Hofstaetter3,4, S. Smolek1,
P.Wobrauschek1, R. Simon5, R. K. Fuchs6,9,
M. R. Allen6, K. W. Condon6, S. Reinwald6, D. McClenathan7, B.
Keck7, R. J. Phipps7, D. B. Burr6,9, P. Roschger3, E. Paschalis3,
K. Klaushofer3, C. Streli1
1 Atominstitut, Technische Universitaet Wien, Stationallee 2, 1020 Vienna, Austria
Stanford Synchrotron Radiation Lightsource, 2575 Sand Hill Road, Menlo Park, CA 94025, USA
3 Ludwig Boltzmann Institute of Osteology at the Hanusch Hospital of WGKK and AUVA Trauma Centre Meidling,
Hanusch Hospital, 1140 Vienna, Austria
4 Department of Orthopaedic Surgery, Vienna General Hospital, Medical Univ. of Vienna, 1090 Vienna, Austria
5 Forschungszentrum Karlsruhe GmbH, Institute for Synchrotron Radiation, Hermann-von-Helmholtz-Platz 1, D76344 Eggenstein-Leopoldshafen, Germany
6 Department of Anatomy and Cell Biology, Indiana University School of Medicine, Indianapolis, IN, USA
7 Procter and Gamble Pharmaceuticals, Mason, OH, USA
8 Department of Physical Therapy, School of Health and Rehabilitation Sciences, Indiana University, Indianapolis,
IN, USA
9 Department of Orthopaedic Surgery, Indiana University School of Medicine, Indianapolis, IN, USA
2
Seite 44
22
Distribution of trace elements in Sr treated
rat bones
Analysis:
Motivation:
•
It is not entirely clear where exactly
Sr is incorporated in bone during
treatment.
•
•
•
•
Using confocal SR micro-XRF
analysis in an ovariectomized rat
model of osteoporosis, our goal
was to evaluate
1. where in the trabecular bone
tissue Sr is incorporated
during systemic treatment and
2. if the incorporation of Sr into
the bone matrix is altered in
case of a calcium deficient diet
compared to a normal diet.
•
•
•
•
•
•
First (surface near) layer of the
sample
Recording of three to five maps per
sample
Areas of 300 x 300 µm² to
850 x 850 µm²
Spectra evaluation (AXIL)
Normalization to cps and 100 mA
ringcurrent
Generation of element maps (heat
scale)
Segmentation of µ-XRF images
using principal component analysis
and k-means clustering.
Comparing Sr/(Sr+Ca) for each
cluster to identify the treatment
groups.
Unblinding of measured samples
Seite 45
SR-µXRF Sr in bone
• Sr treatment in cases of Osteoporosis to improve
production of bone material
• Where is Sr STORED IN BONE?
• Influence of diet Ca levels on Sr uptake?
• 5 Groups:
–
–
–
–
–
Group 1: untreated Control group
Group 2: low Sr Dose, normal Ca diet
Group 3: low Sr Dose, low Ca diet
Group 4: high Sr Dose, normal Ca diet
Group 5: high Sr Dose, low Ca diet
Seite 46
23
SR-µXRF Sr in bone
Untreated
Control group
Low Sr Dose,
low Ca diet
Seite 47
SR-µXRF Sr in bone
High Sr Dose,
normal Ca
diet
High Sr Dose,
deficient Ca
diet
Seite 48
24
SR-µXRF
Sr in bone Conclusions
• Sr is located and built in the new bone
matrix
• Almost no Sr in old bone
• The groups could be successful
correlated by their ratios Sr/(Sr+Ca) .
• Highest Sr countrates at high Sr Dose and
deficient Ca diet -> Ca deficient diet
leads to high incorporated Sr.
Seite 49
ATI µXRF Spectrometer
Phytoremediation
• Phytoremediation: Extraction of metallic
contaminations from soil by plants
• Determination of the Elemental distribution in the
leaves of Dittrichia viscosa growing in the tail
region of the mines
• Comparison with a control group
In collaboration with E. Marguí, Laboratory of X‐ray Analytical Applications (LARX).
Institute of Earth Sciences “Jaume Almera”, CSIC. Solé Sabarís s/n. 08028 Barcelona,
Spain
25
Phytoremediation
(Pb, Zn)
ATI µXRF Spektrometer
Phytoremediation
Control group
Seite 52
26
Phytoremediation
• Metals accumulate in „Hot-Spots“
• Significant higher Intensities in leaves from
contaminated regions compared to the
control group
• Correlations of metals found from
contaminationen in leaves
Seite 53
27
Seite 55
28
PART (Portable ART Analyzer)
An X-Ray Spectrometer for special
applications in Cultural Heritage.
G. Buzanich1,6, P. Wobrauschek1, C. Streli1, A. Markowicz2,3, D. Wegrzynek2,3,
E. Chinea-Cano2, M. Griesser4, K. Uhlir4, A.Guilherme5, M. Radtke6, U.Reinholz6,
H. Riesemeier6
1) Technical University of Vienna, Atominstitut, Stadionallee 2, 1020 Vienna, Austria
Agency’s Laboratories Seibersdorf, International Atomic Energy Agency, 2444 Seibersdorf, Austria
3) AGH University of Science and Technology, Faculty of Physics and Applied Computer Science,
Department of Radiometry, Al. Mickiewicza 30, 30-059 Krakow, Poland
4) Conservation Science Department, Kunsthistorisches Museum, Burgring 5, 1010 Vienna, Austria
5) Centro de Física Atómica da Universidade de Lisboa. Av. Prof. Gama Pinto, 2. 1649-003 Lisboa,
Portugal
6) BAM Federal Institute for Materials Research and Testing, Richard Willstätter Str. 11, 12489 Berlin,
Germany
2)
58
29
Portable ART analyzer
(PART I & II)
In cooperation with Kunsthistorisches Museum Wien and IAEA
PART I
Saliera B. Cellini 1540-43 produced
• 50kV/1mA Pd x-ray
tube
• Polycapillary x-ray
optic (160µm) or
collimator (1mm)
• Ketek SDD, 10mm²,
8µm Be
• Vacuum chamber
G. Buzanich, P. Wobrauschek, C. Streli, A. Markowicz,
D. Wegrzynek, E. Chinea-Cano, S. Bamford,
Spectrochimica Acta Part B 62 (2007) 1252 –1256
K. Uhlir, M. Griesser, G. Buzanich, P. Wobrauschek,
C. Streli, D. Wegrzynek, A. Markowicz, E. ChineaCano, X-Ray Spectrom. 2008; 37: 450–457
30
PART II: Components
• Exchangeable x-ray tube
(Mo /Cr) 50W
• Polycapillary x-ray optic
(XOS), 145µm for Cr-Kα
(5.41 keV)
• Ketek SDD, 20mm², 8µm
Be
• Vacuumchamber
G. Buzanich, P. Wobrauschek, C. Streli, A.
Markowicz, D. Wegrzynek, E. Chinea-Cano, M.
Griesser and K. Uhlir, X-Ray Spectrom. 2009;
39: 98-102
PART II: Setup
• Spectrometer
motorized positioning
(200 mm / 300 mm /
1000 mm depth x
width x Height)
• Stable design of
stand
• User friendly control
Seite 62
31
Accessibility of concave objects
PART I
PART II
63
X-ray physics@ Atominstitut
FWF
IAEA: Bolivien, Jamaica,
Sri Lanka,Jordanien
KFKI-Budapest
Univ Hamburg
Eötvös Univ.
Budapest
FBK-Trento
HASYLAB
ANKA
SSRL
( PW)
MPI f. Colloidf. Berlin
L.Boltzmann Inst f
Osteologie, Wien
Synchrotron
radiation
ANNA:
I3- EC Project
FBK+11 partners
TXRF
GIXRF
2D imaging
XAS
3D imaging
µ-XRF
Fluo-tomo
GEXRF
TXRF-Akkr-golden lab
XRS
X-ray tube
excited
XRF
Phase contrast
imaging- SIT
Portable XRF
IAEA
art analysis
KHM
Seite 64
32
XRS team 2010
Seite 65
33

Die Anwendung der Röntgenstrahlung in den Umwelt- und

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