nuclear material characterization: cea/dam ile de france … · 2015-11-05 · nuclear material...
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1 OCTOBRE 2015 | PAGE 1CEA | 10 AVRIL 2012
Nuclear material characterization: CEA/DAM
Ile de France capacities.Focus on SIMS analysis
Anne-Laure FAURÉ, Fabien POINTURIER, Olivier MARIE , Amélie HUBERT, Anne-
Claire POTTIN, Maxime BRIDOUX
CEA, DAM, DIF, F-91297 Arpajon, France
NKS-B Seminar on Nuclear Forensics in Nordic Countries 5th – 6th October 2015
Table of contents
Overview of CEA/DAM Ile de France capacitiesBulk analysisOrganic compound characterizationParticle analysis
Focus on SIMS (Secondary Ion mass Spectrometry) Description of the instrumentDescription of sample treatmentDescription of the SIMS particle analysis processAdvantages and drawbacks
Some applications of SIMS in the field of nuclear m aterial characterization :Presentation of the results obtained for the CMX-4 exercice organized by NF-ITWGMeasurement of fluorine in micrometric uranium particlesGeolocation of uranium via oxygen measurement in micrometric uranium particles?
Links between CEA and nordic countries
Conclusion
| PAGE 1/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Table of contents
Overview of CEA/DAM Ile de France capacitiesBulk analysisOrganic compound characterizationParticle analysis
Focus on SIMS analysis (Secondary Ion mass Spectrom etry) Description of the instrumentDescription of sample treatmentDescription of the SIMS particle analysis processAdvantages and drawbacks
Some applications of SIMS in the field of nuclear m aterial characterization :Presentation of the results obtained for the CMX-4 exercice organized by NF-ITWGMeasurement of fluorine in micrometric uranium particlesGeolocation of uranium via oxygen measurement in micrometric uranium particles?
Links between CEA and nordic countries
Conclusion
| PAGE 2/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Some history about CEA/DAM Ile de France
| PAGE 3/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Environment Survey of
Nuclear test Sites
1996
2001
2010Environment
Monitoring of French CEA military division
centers
IAEA NWAL for environment samples for bulk and particle
Analysis of higher amounts of NM
( > 100 mg)
Specificity of the laboratories: capability to perform tra ce analysis inenvironmental samples → adaptation of this expertise in the nuclearmaterial characterization when low amounts of material is av ailable.
Mururoa
Bulk analysis : precise isotopic ratios and quantif ication of U and Pu at trace level
| PAGE 4/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Uranium and Plutonium measurements by MC-ICP-MS (Neptune Plus, Thermo):
High sensitivity: >1.2 V/ppbMeasurement of 236U/38U isotopic ratio
below 10-7 for a 1ppb solution,Detection limit for Pu below 0.5 fg
(1fg=10-15g).
Chemical treatment: Total dissolution of the sample by acid digestion,Addition of tracers (233U and 244Pu) for isotopic
dilution,Separation, concentration and purification of U
and Pu by ion exchange chromatography.Great care to protect samples from
contaminations (cross contamination, atmosphere,glassware…)
6
226Ra1599 y
206Pbstable
Decay chain of the 238U
Uranium extraction and refining The clock is set to zero
From Bourdon et al. (2003) Introduction to U-series Geochemistry – Reviews in mineralogy & geochemistry Vol 52
238U4,5x109 y
234U2,45x105 y
234Th24,1 d
230Th7,5x104 y
Starting of the chronometer
During chemical purification, daughter isotopes are discarded
Micro-colonne
(100 µL of resin bed)
Results of REIMEP 22 interlaboratory comparison on the age determination of a young uranium material (below 2 years)
Bulk analysis : age dating
| PAGE 5/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Pointurier et al, Journal of Radioanalytical Nuclear Chemistry, 2013, 296, 593-598
Varga et al, Applied radiation and Isotopes, 2015, 102, 81-86
| PAGE 6/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Bulk analysis : REE pattern
Each uranium ore type gets aspecific REE pattern (dependingon the geological origin). The REEpatterns remain unaltered fromuranium ores to uranium oreconcentrates (UOC).
Chemical treatments onchromatography resins1) to remove uranium2) to concentrate REE
REE measurements on a quadrupole ICP-MS (“X Series”, T hermo)Need for an internal spike to obtain precise concentrations (no need if only REE pattern is requested)
LD < ppb (1 ng/g U)
100 mg UOCdissolution in PFApre-cleaned vials
From Varga et al, Radioachimica Acta, 2010, 98, 771-778
| PAGE 7/38
ChargePolymerbinders
Oils / wax-likecompounds
Additives (plasticizers)
Uranium processing may include solvent extraction using a variety of organic solvants.Uranium can also be associated with explosive materials (nuclear weapon), fiberreinforced materials.The identification of these products provides useful informat ion about the productionprocess and/or origin of the nuclear material.
Organic compound analysis : detection of trace polymerresidues, solvents or explosives
Direct analysis by Orbitrap
Extraction by TwisterTM
followed by Gas Chromatography
Bridoux et al, Analytica Chimica Acta, 2015, 869, 1-10
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Fundamentals on Particle Analysis
Need of sensitive techniques 1) to detect uranium particles and 2) to measure isotopic ratios on individual uranium particles.
| PAGE 8/38
A way to detect proliferation without having access to the nuclear material
Particle emitted by declared activity
Particle emitted by undeclared activity
Non declared workshop on a
declared facility
Particle sampling(swipe samples)
Safeguards Laboratory of IAEA : coding, sending to NWALs
Map of the NWALs
Micrometric particles coming from a nuclear facility have an uranium isotopic composition characteristic of the industrial process .
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
Detection of Uranium bearing particle among thousan ds of other particles, mainly dust particless
| PAGE 9/38
Scanning electron microscope (SEM) : Use of anautomated particle detection sofware, “Gun Shot Residue” toidentify U particles thanks to EDX analysis. No information onthe U isotopic composition.
U
Fission Track (FT) : Irradiation of samples under wellthermalized neutron flux to induce U/Pu fission. Information onthe size of the particle or 235U abundance.
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
Detection of Uranium bearing particle among thousan ds of other particles, mainly dust particless
| PAGE 10/38
Secondary Ion Mass Spectrometry (SIMS) : Use of an automated particledetection software, Automated Particle Measurement. Estimation of the 235Uabundance. (See after)
CAMECA IMS 7F (Gennevilliers, France)
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Precise isotopic composition measurement
| PAGE 11/38
Thermal Ionization Mass Spectrometry (TIMS)
Secondary Ion Mass Spectrometry (SIMS)
Thermo Triton (Bremen, Germany)
TIMS filament
0,000001
0,00001
0,0001
0,001
0,01
0,1
1
0,001 0,01 0,1 1 10
234 U
/238 U
235U/238U
Natural Natural
Low Enriched
UraniumNatural Natural
Uranium
Low Enriched
Uranium
High Enriched
Uranium
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
| PAGE 12/38
500 1000 1500
Raman sh ift / cm-1
0
1000
2000
3000
4000
5000
6000
7000
Co
un
ts
185 cm-1
351 cm-1 412 cm-1
487 cm-1 810 cm-1
Peaks due to the carbon support
a)
500 1000 1500
Raman shift / cm-1
0
10000
20000
30000
40000
50000
Co
un
ts
823 cm-1 867 cm-1b)
500 1000 1500
Raman shift / cm-1
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
Co
unt
s
c)845 cm-1 1052 cm-1
500 1000 1500
Raman shift / cm-1
5000
10000
15000
Co
unts
867 cm-1
184 cm-1
259 cm-1
d)
150 cm-1
500 1000 1500
Raman shift / cm-1
0
100
200
300
400
500
600
700
800
Co
unt
s
815 cm-1e)
500 1000 1500
Raman shift / cm-1
0
500
1000
1500
2000
Cou
nts
f) 712 cm-1 810 cm-1
U3O8 UO4 UO3
UO2F2 UF4 ADU
Identification of U chemical phases
Raman Renishaw
“In Via” spectrometer
Raman spectrometer
associatedwith SEM
Uranium Ores
Uranium Ore concentrates
UO3, UF4UF6, UO2F2
U, UO2
U3O8
Main uranium compounds encountered during the different steps of the fuel cycle
Other U particle characterization : µ-Raman spectrometry
Measurement on individualparticle with µ-Raman afterSEM localization
Possible coupling with a SEMfor micrometric particlesanalysis (≥ 2 µm).
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Pointurier and Marie, Journal of Raman Spectroscopy, 2013, 44, 12, 1753-1759
Table of contents
Overview of CEA/DAM Ile de France capacitiesBulk analysisOrganic compound characterizationParticle analysis
Focus on SIMS (Secondary Ion mass Spectrometry) Description of the instrumentDescription of sample treatmentDescription of the SIMS particle analysis processAdvantages and drawbacks
Some applications of SIMS in the field of nuclear m aterial characterization :Presentation of the results obtained for the CMX-4 exercice organized by NF-ITWGMeasurement of fluorine in micrometric uranium particlesGeolocation of uranium via oxygen measurement in micrometric uranium particles?
Links between CEA and nordic countries
| PAGE 13/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
Principle and Instrumentation
| PAGE 14/38
Magnetic Sector
DetectionSample
Secondary Ions to be analysed
PrimaryIons
Electrostatic SectorSource
Principle : Bombardment of a sample surface with pri mary ions followed by mass spectrometry measurement of the emitted second ary ions.
Some information on basics and instrumentation can be found on the following links: SIMS Theory Tutorial from Evan Analytical Group(www.eag.com)SIMS Tutorials from the School of Geosciences, University of Edimburgh(www.geos.ed.ac.uk)
High vacuum : 10 -8-10-10 mbarNKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
SIMS Cameca 7F
| PAGE 15/38
Principle and Instrumentation
Cesium source : light elements (C,
N, O, F…)
Duoplasmatron source : U, Th, Pu
Electron gun: analysis of insulated sample
Detection block: Electron multiplier, Faraday cup,
channelplate
CAMECA IMS 7F (Gennevilliers, France)
Chamber
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Magnetic sector
1 OCTOBRE 2015
Sample treatment for particle analysis
Swipe sample containing
particles
Particle extraction by sucking up (Vacuum impactor)
Particle extraction is
performed inside a
laminar flow box (in a
disposable glove bag
when using the vacuum
impactor technique)
Carbon disk
Swipe sampleParticle extraction Carbon
planchet
SIMS Cameca 7F
| PAGE 16/38
Powder
Particle extraction by means of a plastic tip
1 cm
Suspension in a
solvent (ethanol,
heptane)
Sampling of particle s
with a plastic tip
Loading on
carbon planchet
Carbon planchet
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
Is@238 per pixel (cps)
1 Particle localization using APM
software (duration ~ 12h)
Is@238 per field (cps)
Principle: acquisition of ionic images of 235U and 238U
Data treatment to set the particle
boundaries
Achievement of
the coordinates of
the particles and
the distribution of
the 235U
abundances
Selection of particles of interest
for precise microbeam
measurements
SIMS particle analysis process
| PAGE 17/38
2
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Focus on particle selection from APM result
What are the aims of APM ? 2 cases: 1) The sample contains just a few uranium particles : APM helps to find these particles and to get their coordinates2) In some samples, thousands of uranium particles can be detected. APM helps to select particles among the main isotopic composition and the extrema.
0 0 0 0 0 0 0 0 1 0 0 0 4 3 0 3 2 3 4 102042
113
282
503
690
816
718
524
308
186
118
675432212715 7 10 5 2 4 0 1 0 0 1 0 0
0
100
200
300
400
500
600
700
800
900
0.0
-0.1
0.2
-0.3
0.4
-0.5
0.6
-0.7
0.8
-0.9
1.0
-1.1
1.2
-1.3
1.4
-1.5
1.6
-1.7
1.8
-1.9
2.0
-2.1
2.2
-2.3
2.4
-2.5
2.6
-2.7
2.8
-2.9
3.0
-3.1
3.2
-3.3
3.4
-3.5
3.6
-3.7
3.8
-3.9
4.0
-4.1
4.2
-4.3
4.4
-4.5
4.6
-4.7
4.8
-4.9N
um
be
ro
f p
art
icle
s
235U abundance (at.%)
Characterization of these
particles to determine
precisely the 235U minimum
abundance
Characterization of these
particles to determine
precisely the 235U maximum
abundance
Characterization of some of
these particles to determine
precisely the 235U main
abundance
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 18/38
1 OCTOBRE 2015
3 Microbeam measurementSelection of particles of interest for
precise microbeam
measurements
SIMS particle analysis process
| PAGE 19/38
2
235U 1H 236U +
238U 1H
238U
235U
234U
100 200 300 400Time, s
1e2
1e3
1e4
1e5
Inte
ns, c
/s
IMS701 - CEA 09/21/2015, 09:35Sample: NBS 100 Depth ProfileData file: D:\Cameca IMS Data\Analyses\Standard\NBS U100 N2\2015\21-09-2015\NBS100-21092015#1.dpRecipe: No_name_2.rdpDuo+ Ie: 10000eV Ip: 2.39e-01/2.30e-01nA Raster: 0um DT: Off Gate: 100%P: 3.3e-10mbar SpleHV: +5000V MR: 400 FA: 1800um CD: 400um DeltaE: 75eVComments:
234U
235U
235U 1H
238U
238U 1H
0,000001
0,00001
0,0001
0,001
0,01
0,1
1
0,001 0,01 0,1 1 10
234 U
/238 U
235U/238U
Natural Natural
Low Enriched
UraniumNatural Natural
Uranium
Low Enriched
Uranium
High Enriched
Uranium
Achievement of all precise isotopic
compositions of U particles
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
SIMS particle analysis : advantages and drawbakcs
Advantages Drawbacks
Space resolution of a few µm , down to 50 nm (NanoSIMS)
Isobaric interferences
Low detection limits down to ppblevel (1µg/kg)
Matrix effect
In situ analysis Low roughness ( < a few microns)
Very low sample consumption (maybe less than 1 µm3)
Planeity
Large panel of analysis : Isotopicand elemental measurements, ion images, depth profiling
Samples must be compatible withhigh vacuum
IMS 1280 IMS 7FIMS 1280NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 20/38
SIMS particle analysis : new generation of instrume nts
IMS 1280
IMS 1280
Size × 5
The LG-SIMS (or IMS 1280) : new generation of SIMS instrument enablingSimultaneous detection of all uranium isotopes (ion multi-collection)Removal of most of the isobaric interferences (high mass resolution)
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 21/38
IMS 7FThe NanoSIMS : state of the art of ionic images with a lateral reso lutionof 50 nm.
Left SEM images of UO2 particles. Right nanoSIMS ion image of 16O in UO2 particles. From Lawrence Livermore National Laboratory, USA
1µm
NanoSIMS
The place of SIMS in the analytical procedure of n uclear material
Need of very low amount of material: sampling can be performed at the beginning of the c haracterization- For bulk material, particle sampling by wipping the surface or loading of some
fragments of the material. - For powder material, sampling with a plastic tip.
SIMS can be used as a “screening technique”
Be careful with the tools used for sampling because it can lead to interferences for further analysis
Metallic tools can leave metallic particles that can be detected for instance by SEM or by ICP-MS after chemical treatment.Plastic tools can leave organic particles than can be detected for instance by organicmass spectrometric techniques.
More generally, it is recommended to use very high qual ity reactants and inertrecipients (like PTFE vials) to minimize the risk of con tamination and to have a quite well-established analytical procedure before any sa mple manipulation.
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 22/38
Table of contents
Overview of CEA/DAM Ile de France capacitiesBulk analysisOrganic compound characterizationParticle analysis
Focus on SIMS (Secondary Ion mass Spectrometry) Description of the instrumentDescription of sample treatmentDescription of the SIMS particle analysis processAdvantages and drawbacks
Some applications of SIMS in the field of nuclear m aterial characterization :Presentation of the results obtained for the CMX-4 exercice organized by NF-ITWGMeasurement of fluorine in micrometric uranium particlesGeolocation of uranium via oxygen measurement in micrometric uranium particles?
Links between CEA and nordic countries
| PAGE 23/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Presentation of the CMX-4 exercice
Fourth exercice organized by the Nuclear Forensics Interna tional Technical WorkingGroup (NF-ITWG)
Objective of ITWG: ITWG is a working group of experts including scientists, lawenforcement officiers, first reponders and nuclear regulators. Their aims are toprovide assistance and technical solutions on the field of nuclear forensics to nationalor international authorities.4th Comparative Material Exercice (CMX-4) : 3 uranium samples were provided toparticipating laboratories. The 16 labs were asked to provide information related tothe 3 samples based on an exercice scenario.
| PAGE 24/38
ES1 ES2 ES3
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Description of the samples: two pellets and one powder sampl e
Particles were extracted by means of a tip (ES1) or by wiping the surface of the pellets with a cotton cloth (ES2 and ES3). Particles were loaded onto carbon planchet with the vacuum impactor technique.
First results: Distribution of the 235U abundances given by APM
| PAGE 25/38
Cluster A Cluster B Cluster C
First results : Distribution of the 235U abundances
What information does APM brings?“Bell-shape” distributions which centers are in good agreement with the analysis of macroscopic amounts of materials (“bulk” measurements carried out by ICP-MS).
Possibility to compare the main 235U abundances : Average 235U abundances ofES1 and ES3 are very close and largely different from the average 235U abundance ofES2.
What more? Detection of depleted uranium in two samples, detection of low enriched uranium up to 4% 235U in all samples. APM analysis is a mean to detect a large range of isotopic composition at particle level.
APM results: ES1 ES2 ES3
Maximal 235U abundance (%) 4.73 ± 0.29 3.77 ± 0.41 4.26 ± 0.25
Minimal 235U abundance (%) 0.89 ± 0.09 0.41 ± 0.13 0.49 ± 0.08
Average 235U abundance (atomic %) 2.70 ± 0.30 1.83 ± 0.35 2.55 ± 0.35
Number of particles 4 596 910 915
| PAGE 26/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Second results: precise isotopic abundances of part icles coming directly from the samples (about 40 particles per sample)
What additionnal information do we obtain with minor isotope measurements (234U, 236U) ?
From 234U/238U vs 235U/238U : alignment of all ratios, forming « enrichment lines » .
This lines depend on the « feed » : NU, DU, RU
Detection of 236U in some particles means that uranium was irradiated.
| PAGE 27/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Last results: analysis of particles coming from the outside of the ultimate bag of the nuclear material samples
Description of the sample packaging:
Particles coming from the outside of the ultimate bag were extracted by wiping thesurface of the bag with a cotton cloth. Particles were loaded onto a carbon disk with thevacuum impactor technique.
++
Ultimate bag
Inner container
ES1 ES2 ES3
| PAGE 28/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Last results: Comparison of the isotopic compositio n of the particles coming from the samples and the outside o f the ultimate bag
What does SIMS analysis reveal?General agreement between the isotopic composition of particles coming from the samples and the ultimate bags: The isotopiccomposition of the threesamples can be estimatedwithout opening the ultimatebag.
Only one particle coming from the ultimate bag of ES2 has an isotopic composition which is not consistent with the ones of the three materials. Samples werepacked in another facility? In case of « real » material seized, these analyses can help to identify the places where the material was stored or handled, from its origin to the place where it was seized.
| PAGE 29/38
235U: 7.0 ± 0.1 %
Detection of fluorine in micrometric uranium partic les : a way to detect a conversion activity
Detection of fluorine → signature of a conversion and/or enrichment activity
Uranium isotopic measurement + fluorine detection → discrimination between natural uranium (ore or yellow cake), conve rted uranium and enriched uranium
Fauré et al, Journal of Analytical Atomic Spectrometry, 2014, 29, 145-161 1 OCTOBRE 2015
| PAGE 30/38
Initial steps of nuclear fuel cycle with natural uranium
0
56
0,7
% 235U F/U (atomic ratio)
Civil purposes
Military purposes
Ore
Yello
wca
keC
onve
rsio
n
Enr
ichm
ent
Nuc
lear
Fue
l P
ower
Pla
nt
4UF4
UF6
0
56
0,7
% 235U F/U (atomic ratio)
Civil purposes
Military purposes
Ore
Yello
wca
keC
onve
rsio
n
Enr
ichm
ent
Nuc
lear
Fue
l P
ower
Pla
nt
0
56
0,7
% 235U F/U (atomic ratio)
Civil purposes
Military purposes
Ore
Yello
wca
keC
onve
rsio
n
Enr
ichm
ent
Nuc
lear
Fue
l P
ower
Pla
nt
4UF4
UF6
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
1 OCTOBRE 2015
Ion images of UF4 particles
Development of a database by measuring the relative amount of fluorine in particles from Uranium Ore Concentrate materials (CETAMA, France), conversion plant workshop, UF4 material (CRM 17B, NBL, USA)
Detection of fluorine in micrometric uranium partic les : a way to detect a conversion activity
Fluorine is easily detectable at the mass correspon ding to 238U19F with the DUO source.Advantage of detecting fluorine at 238U19F mass instead of 19F mass : 1) more confidence that fluorine is chemically linked to uranium, 2) UF+ sensitivity is better thanF+
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 31/38
Use of the database to compare the relative amount of fluorine measured in real-lifeparticles coming from inspected nuclear facilities.
When a natural uranium composition is measured, the relativ e fluorine amountmeasurement provides additionnal information on the indus trial origin of thenuclear material.
1E-03 1E-02 1E-01 1E+00
UF/U ion intensity ratio
CP 1
CP 2
swipe sample
UOC UF4
What can beconcluded? Uraniumwas converted at onepoint before thesampling but was notenriched.
Some applications (1/2) : « real-life » swipe sample in the Safeguards field
Fluorine measurements are routinely done for IAEA samples since 2014.
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 32/38
1 OCTOBRE 2015
Environmental samples coming from outside of the conversion plant buildings (CP1 and CP2) :
What can be concluded? High level of fluorine was detected in particles collectedoutside of the building of the conversion facility even if 4 years elapsed betweenthe sampling date and the analysis.
1E-04
1E-03
1E-02
1E-01
1E+00U
F/U
ion
inte
nsity
ratio
Am
éthy
ste
CR
M U
F4
Gre
nat
Cal
cédo
ine
Mor
ille
Cha
nter
elle
Bol
et
CP
1
CP
2
CP
Pur
if.
CP
Flu
or.
UOC
Conversion facility
UF4
Some applications (2/2) : persistence of fluorine m arking in environmental samples
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015 | PAGE 33/38
Geolocation of uranium via oxygen measurement in micrometric uranium particles?
1 OCTOBRE 2015
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Process waterRain water Groundwater Uranium oxide?
Natural isotopic fractionning
(GNIP AIEA/WMO 2006)
(http://serc.carleton.edu/microbelife/research)
Need for high precision methods to distinguish clos e geographic areas
Oxygen isotopic ratio is easily measurable by SIMS using Cs primary ions with an external precision of ~ 0,1 %. So in theory, SIMS is suitable for these analysis but…
| PAGE 34/38
Geolocation of uranium via oxygen measurement in micrometric uranium particles?
1 OCTOBRE 2015| PAGE 35/38NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Crushing, chemical purification, liquid extraction, washing, precipitation, drying…
Source of oxygen: Water, Air, Acid….
Agaric
(UOC)
Grinding
Granulometry
Roasting
Acid impregnation
Drying
Calcination
Homogenization
Morille
Morille (UOC CRM, Cetama) production process
Best way to answer the first question: sampling an industrial process at every step.
While waiting for such samples, measurement of the oxygen composition of UOC sample after different treatments inspired by the production of one CRM sample called Morille from CETAMA.
Before any geolocation attempt, the first question to answer is “ where does the oxygen in uranium oxyde come from?”
Particle sampling aftereach treatment
Uranium Ore Concentrate
Geolocation of uranium via oxygen measurement in micrometric uranium particles?
1 OCTOBRE 2015
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Preliminary results : Each treatment affects the isotopic ratios, mainly thermal treatment at high temperatures.
1,92E-03
1,94E-03
1,96E-03
1,98E-03
2,00E-03
2,02E-03
2,04E-03
2,06E-03
2,08E-03
Agaric After roasting After acidimpregnation
After drying Aftercalcination
18O
/16 O
Conclusion of Jonathan Plaue, University of Nevada, in his thesis “Forensics signatures of chemical process history in uranium oxyde: “[…] Oxygen isotope ratios in the real‐world samples neither directly correlate with the oxygen isotope ratios of local meteoric water nor support a consistent alternative fractionation. […] the real‐world variability in particle sizes and time at temperature profiles is sufficien t to complicate interpretation oxygenisotope ratios in U3O8 samples as a reliable geolocation signature. […]”
Post conversion U compounds may be more suitable fo r geolocation via oxygen isotopic composition.
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Links between CEA/DAM Ile de France and Nordic coun tries regarding nuclear material and environmental samp le analyses
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2015 : Following the CMX-4 exercise, redaction of a paper on the use of µ-Raman spectrometry and DRX for the chemical phase identif ication.
Participation of CEA/DAM Ile de France and CEA Vald uc, the Swedish DefenceResearch Agency (FOI), the Australian Nuclear Scie nce and Technology Organization (ANSTO) and the South African Nuclear Energy Corporation (NESCA)
2012 : Collaboration on the characterization of PuO 2 particles produced by VTT in the framework of an IAEA support action for Safeguards purposes.
Participation of CEA/DAM Ile de France and the VTT Technical Research Center of Finland
2012 : Training of a young scientist from VTT, Finla nd on ICP-MS
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015
Conclusions
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CEA/DAM Ile de France developed /is developing a large panel of methodologies tocharacterize nuclear material:
From milligrams amounts down to the micrometric particle scaleBoth qualitative (U chemical form, …) and quantitative (Pu amounts, …)
SIMS is a technique that is particularly suited for to the characterization of nuclear material :Possibility to measure almost of all the elements of the periodic tableHigh sensitivity : analysis of individual micrometric particlesVery low sample consumption : almost non destructiveCapability to characterize particles of nuclear material c ollected on the packagingCapability to characterize irradiated nuclear material in shielded instrument (CEACadarache)
To conclude on SIMS , it has its place in the analytical techniques to implement in a labthat needs to characterize nuclear material.
To further increase the knowledge on nuclear material chara cterization :Collaborations between countries, institutes, round robin exercices are essential forscientific exchanges.Development of reference material is also required to develop and validate newmethodologies. In 2015, a new UOC CRM “Feldspath” (CETAMA, France) has beenqualified (REE, impurities).
NKS-B Seminar on Nuclear Forensics in Nordic Countries | 5th – 6th October 2015