Hungarian Academy of Sciences
Institute of Isotopes
Laboratory for nuclear
forensics and
environmental analysis
Presented by:
Éva Széles
Seminar on
R & D Activities at the Institute of Isotopes Related to Nuclear Security
February 19, 2010, Vienna
www.iki.kfki.hu
Main Tasks of the Laboratory
– nuclear forensics
Hungarian Academy of Sciences
Institute of Isotopes
 Analysis of confiscated nuclear materials
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characterization and identification of the found and
confiscated samples with unknown origin
destructive and non-destructive analysis
analysis of U and Pu
 e.g. precise isotope ratio measurements
 Analysis for safeguards purposes
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environmental and swipe samples
single particle analysis by laser ablation ICP-MS
(LA-ICP-MS)
environmental monitoring for safeguards purposes
before the decomissioning of nuclear facilities
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Main Tasks of the Laboratory
- other aspects
Hungarian Academy of Sciences
Institute of Isotopes
 Analysis of environmental samples
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Measurement of low-level actinides in environmental
samples (soil, sediment, water, plant, etc.)
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Analysis of alternative nuclear materials (Am, Np, Cm)
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Direct analysis of solid samples by LA-ICP-MS
technique (e.g. geological samples, uranium ore samples,
metal samples, etc.)
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
Applied Techniques
Main instruments:
 High resolution inductively coupled plasma sectorfield mass spectrometry (ICP-SFMS)
 High resolution gamma spectrometry (HRGS)
 Scanning electron microscope (SEM/EDX)
 Neutron coincidence counting (NCC)
Additional techniques:
 X-ray diffraction analysis (XRD)
 Prompt-gamma activation analysis (PGAA)
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
 ELEMENT2 with single collector
Hungarian Academy of Sciences
Institute of Isotopes
High-resolution inductively coupled plasma
sector-field mass spectrometer (ICP-SFMS)
 Installed in a clean room
(Class 100 000)
 Various sample introduction systems:
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Stable sample introduction
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Laser ablation system
 Sample preparation laboratory (Class 10 000):
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With a Class 100 laminar flow hood
Ultra-trace level measurements
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Laser ablation (LA) unit for the mass
spectrometer
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Hungarian Academy of Sciences
Institute of Isotopes
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Quasi non-destructive measurement
no chemical sample preparation needed
short analysis time
(typically <1 h/sample)
Laser ablation system:
UP213 (New Wave)
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
High-resolution gamma spectrometry
(HRGS)
 Fully non-destructive measurement
 No sample preparation needed
 Low-background gamma spectrometer
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Iron chamber with 20 cm wall thickness
150 cm3 coaxial HPGe detector
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34% relative efficiency
Sample cavity flushed with nitrogen
Planned upgrades:
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Better detector
Underground facility
 Low-energy planar HPGe detectors
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For U and Pu isotopics
N2 flushing
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Scanning Electron Microscope
(SEM)
 Broad magnification range
Hungarian Academy of Sciences
Institute of Isotopes
 Type JEOL JSM-5600LV
up to 300 000
 “Low vacuum” mode for
observing nonconductive
samples in their native
state
 Elemental analysis
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Attached energy dispersive
X-ray spectrometer (EDS)
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
Origin of nuclear forensics in
Hungary
Illicit trafficking in Hungary: since the early ’90s
 In the beginning: only planar HPGe used
 Since then:
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Low-background HPGe
SEM
ICP-MS
NCC
A possible site of illicit trafficking in Budapest
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Nuclear forensic applications at IKI
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Hungarian Academy of Sciences
Institute of Isotopes
 Tested with following nuclear materials:
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Powder (U compounds)
 DA & NDA
Pellets (U oxide)
 DA & NDA
Fuel rods (U oxide)
 NDA
Fuel assemblies
 NDA
Sealed sources (eg. Pu)
 NDA
…
 Non-destructive techniques (NDA) are still needed
though very accurate destructive methods (DA) are available
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
 Selected nuclear forensic
applications developed at the
Institute of Isotopes
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Uranium age dating by destructive
ICP-MS
Hungarian Academy of Sciences
Institute of Isotopes
Determination of production date of
nuclear materials
 Digestion of the uranium-oxide sample
 Determination of
234U-content
by isotope
dilution ICP-MS analysis
 Determination of 230Th-content by isotope
dilution ICP-MS analysis after
extraction-chromatographic separation
 Production of 229Th tracer:
from 233U-solution („milking”)
Uranium age dating by quasi-non
destructive LA-ICP-MS
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
 Two measurements:
Hungarian Academy of Sciences
Institute of Isotopes
Uranium age dating by
fully non-destructive HRGS
 234U/238U
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by planar HPGe
214Bi/238U by coaxial HPGe
in low background
 Activity ratios determined by
relative (“intrinsic”) efficiency
calibration
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Independent of measurement
geometry
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Detecting the presence of
reprocessed uranium
-7
232U
10
Reprocessed
U / total U, %
content
indicates
reprocessed
uranium
232
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Hungarian Academy of Sciences
Institute of Isotopes
 232U analysis by HRGS
-8
10
-9
10
-10
10
Not reprocessed
-11
10
0.1
1
10
100
235
232U
content determined
by HRGS as a function
of 235U enrichment
U-enrichment, %
 236U and Pu isotopes can be measured by ICP-MS
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
Rare-earth elements in uranium-bearing materials
determined by ICP-SFMS – Origin assessment
Three uranium ore concentrates originating from different mills in
order to compare their REE profiles after digestion of the samples
and separation of the matrix (U)
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
Trace elements in uranium-oxide determined
by ICP-SFMS – Origin assessment
Trace element analysis in 3 confiscated
uranium-oxid pellets 
Joint analysis with Institute for
Transuranium Elements (ITU)
Samples:
 590: Natural (HU-NAT)
 642: LEU (HU-LEU)
 643: DU (HU-DEP)
Laboratory for nuclear forensics and environmental analysis
sample 590
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Vienna, February 19, 2010.
Quality assurance
Hungarian Academy of Sciences
Institute of Isotopes
 ISO 9001:2000
 ISO/IEC 17025 – accreditation of the
ICP-MS laboratory is in progress
 Participation in interlaboratory comparisons and
proficiency tests
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ITWG - HEU
REIMEP, NUSIMEP, IAEA-PT
 Joint analysis with JRC ITU, Karlsruhe
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Inter-laboratory comparison (Round
Robin) organised by the ITWG (2001)
 ~1 g HEU sample/lab.
Hungarian Academy of Sciences
Institute of Isotopes
 More than 10 nuclear forensic laboratories participated
Isotopic composition
232U
Average of RR
(7.50±0.55)*10-8
HRGS
LA-ICP-SFMS
234U
235U
236U
238U
0.964 ± 0.055
89.475 ± 1.14
0.661 ± 0.039
8.906 ± 1.22
0.98 ± 0.07
89.8 ± 0.7
0.6 ± 0.1
8.6 ± 0.5
0.965 ± 0.05
90.032 ± 1.30
0.681 ± 0.040
8.322 ± 0.25
Production date
Production date
by HRGS
Production date
by LA-ICP-SFMS
Production date
from Round-Robin
1978 ± 3 years
August, 1979 ± 6 months
Feb-July 1979
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Joint analysis with Institute for
Transuranium Elements (ITU)
Hungarian Academy of Sciences
Institute of Isotopes
 3 uranium oxide pellets from 3 different batches
were analysed at IKI by HRGS and LA-ICP-SFMS
 The pellets were sent to ITU for further
investigation using DA methods
ITU
MC-ICP-MS
IKI
TIMS
IDMS
HRGS
HRGS
LA-ICPSFMS
3.2(9)10-8
232U
234U
0.0346(5)
0.0347(21)
0.0345(33)
0.025(20)
0.0362(24)
0.0358(9)
235U
2.5136(14)
2.5121(14)
2.5119(30)
2.51(12)
2.562(34)
2.529(19)
236U
0.451(22)
0.47(44)
0.47(86)
-
0.38(24)
0.474(24)
238U
97.000(21)
96.9823(20)
96.9829(12)
97.47(12)
97.021(34)
96.961(20)
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
 Safeguards analysis of
environmental samples
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
The laboratory is capable of determining ultra-trace amounts of
uranium and plutonium isotopes and their precise isotope ratios in
environmental swipe samples
Hungarian Academy of Sciences
Institute of Isotopes
Analysis of swipe samples
– bulk analysis
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Analytical procedures developed for bulk analysis:
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Screening by gamma spectrometry
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Microwave digestion instead of ashing
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Extraction chromatographic separation with TRU® column process
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ICP-SFMS measurement
Detection limits achieved:
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Uranium: 0.01 – 5 ng (IAEA SAL req.: 0.1 - 5 ng)
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Plutonium: 1 – 7 fg (IAEA SAL req.: 10 fg)
Special developments: reduction of procedure background
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Clean room facilities
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Optimized procedure
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Sub-boiled acids and minimal chemical consumption
Method was tested by analysis of real swipe samples
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Isotope
IAEA/NWAL
requirements
Detection limit
239
Hungarian Academy of Sciences
Institute of Isotopes
Analytical performance parameters
achieved
Pu
240
Pu
241
Pu
238
U
235
U
234
U
236
U
7.5 fg
Pu ≤ 10 fg/ swipe
2.4 fg
1.1 fg
1 ng
U ≤ 0.1-5 ng/
swipe
11.4 pg
0.14 pg
0.083 pg
Uncertainty of
Isotope Ratios
IAEA/NWAL
requirements
235U/238U
0,23-0,7%
≤ 1%
234U/238U
0,3-3%
≤ 10%
236U/238U
0,3-3%
≤ 10%
240Pu/239Pu
7-10%
≤ 10%
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Development of a novel methodology for the isotopic
composition measurement of single particles
Hungarian Academy of Sciences
Institute of Isotopes
Analysis of single particles by
LA-ICP-MS technique
 Current results: Isotopic analysis of individual uranium
particles by laser ablation ICP-SFMS
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Tested for uranium-oxide particles with different enrichment,
lateral dimensions: down to 10 micron
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Applicable also for low-abundant isotopes (234U, 236U)
Typical precision achieved: 0.2-5% RSD for 235U/238U
Testing for sub-micron particles (JRC IRMM, NUSIMEP)
Particle location: fission track and SEM/EDS
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 Further aim: adaptation of the method for swipe samples
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Analysis of single particles by
LA-ICP-MS technique
Hungarian Academy of Sciences
Institute of Isotopes
LA-ICP-MS measurement
LEU particle (40 x 38 um)
Measured isotope ratios
234U/238U
= (3.78 ± 0.19) × 10-4
235U/238U
= (2.81 ± 0.04) × 10-2
236U/238U
= (4.08 ± 0.08) × 10-3
Laboratory for nuclear forensics and environmental analysis
SEM/EDS
24
Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
Provision for decommissioning of nuclear
facilities - environmental monitoring
Objectives:
 determination of the environmental
contamination baseline/level as
a reference database in the
vicinity of Hungarian nuclear
facilities
 comprehensive environmental monitoring and analysis
before decommissioning for safeguards purposes
 Test measurements at the KFKI site near the research
reactor:
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plutonium and uranium concentrations and isotopic
ratios in soil and wood-moss were determined
Results: Pu: ~fg/g, U: ~ng/g
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Conclusion
characterization of most types of nuclear material
Hungarian Academy of Sciences
Institute of Isotopes
 IKI is capable of a complete nuclear-forensic
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Combined use of DA and NDA instrumentation
 HRGS, ICP-SFMS, SEM, NCC
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Note on Pu: handling only sealed sources
 Only NDA can be applied
 Environmental measurements at ultra-trace level
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Conclusion
Hungarian Academy of Sciences
Institute of Isotopes
 Planned developments:
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Particle analysis with laser ablation ICP-MS
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Upgrading the low-background HRGS facilities
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Possible future application: In-field age dating of
shielded HEU (e.g. of an Improvised Nuclear Device)?
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.
Hungarian Academy of Sciences
Institute of Isotopes
www.iki.kfki.hu
Thank You for Your attention!
Section Head: Dr. András Kovács
Staff:
ICP-MS:
Dr. Tamás Bíró
Dr. Éva Széles
Mr. Róbert Katona
Ms. Zsuzsanna Mácsik
Staff on-leave:
ICP-MS:
Dr. Zsolt Stefánka (HAEA)
Dr. Zsolt Varga (ITU)
HRGS:
Dr. László Lakosi
Dr. Nguyen Cong Tam
Mr. István Almási
Mr. Péter Nagy
HRGS:
Dr. József Zsigrai (ITU)
Mr. János Bagi (JRC Ispra)
SEM: Dr. Péter Hargittai
Laboratory for nuclear forensics and environmental analysis
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Vienna, February 19, 2010.