1 1 "Nuclear analytical chemistry: New challenges and future trends" Analytical innovations for Nuclear Energy Division Frédéric CHARTIER DEN/DANS/Saclay – Départment of Physical Chemistry CETAMA SEMINAR With the participation of analytical laboratories from DPC, DEC, DRCP, DASE, LNHB, UMR Evry, GIS ISAB idf, ISA Lyon, IMEP-LAHC, INP Grenoble … 2 DEN/DANS/Saclay – Department of Physical Chemistry …in response to nuclear challenges
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Innov Analytiques CETAMA 50ans FC [Mode de compatibilit ] · PPT Détecteur conductimétrique (CD) Sortie capillaire (O) IC SC Example : lanthanides separation by isotachophoresis
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"Nuclear analytical chemistry: New challenges and f uture trends"
Analytical innovations
for Nuclear Energy Division
Frédéric CHARTIER
DEN/DANS/Saclay – Départment of Physical Chemistry
CETAMA SEMINAR
�With the participation of analytical laboratories from DPC, DEC, DRCP, DASE,
LNHB, UMR Evry, GIS ISAB idf, ISA Lyon, IMEP-LAHC, INP Grenoble …
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DEN/DANS/Saclay – Department of Physical Chemistry
…in response to nuclear challenges
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… in response to recurrent analytical needs
• Smaller samples (radioactivity...)
• Lower concentrations
• More complex matrices
• Atomic and molecular informations
• Lower levels of effluents and waste
• Faster analysis, cheaper : in-line and on-line
• Field-portable techniques : mobile, robust…
• panoramic analysis, automatic
• specific answer
DEN/DANS/Saclay – Department of Physical Chemistry
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� New challenges, new needs =>
- need to improve analytical performances, analytical conditions…
� Complementary UV-Visible and IRTF spectrometries : speciation in gases .
– Study and kinetic monitoring of chemical reactions – On-line monitoring of industrial processes– In situ analysis of gaseous pollutants– Speciation study in gaseous phase
1. AREVA La Hague Dissolution of spent fuelSelective extraction of element
PROCEDURE :
Trac
e A
naly
sis
DEN/DANS/Saclay – Department of Physical Chemistry
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2. CEA LARC CadaracheMass Concentration mAdditional chemical separations(liquid-liquid extraction, ion exchange chromatography)Isotope ratio measurement (126Sn/124Sn) and 124Sn concentration (standards) by mass spectrometry
3. CEA LNHB SaclayActivity per unit of mass ANuclear counting techniquesGamma spectrometry (126Sn)Liquid Scintillation Counting (79Se)
DEN/DANS/Saclay – Department of Physical Chemistry
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Mass spectrometry : chelating molecules and speciat ionMass spectrometry : chelating molecules and speciat ion
ANALYTICAL SPECIATION : Techniques and methods development to identify and/or quantify chemical species (RN and organic ligands ).
� HPLC/ICPMS and CE/ICPMS coupling : speciation U, Pu, lanthanides
• Basic studies of model systems : Thermodynamic, kinetic data, reactivity, structure…
• Real systems studies (nuclear, environment, biology …) : Species identification, quantification, isotopy, RN oxydation state …
Spe
ciat
ion
=> Separative techniques - mass spectrometry
CE-ICPMS coupling DEN/DPC
Diagramme de spéciation du Puen milieu carbonaté (DAM/DASE/SRCE)
DEN/DANS/Saclay – Department of Physical Chemistry
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⇒ Perspectives : Separative techniques – organic and inorganic mass spectrometryand quantification by isotope dilution
� UHPLC/ESI-MS, LC-MS-MS, ESI-MS coupling :
- Degradation products coming from recycling solvent process
- Extracting molecules impurities identification
- Screening of new extracting molecules
- Thermodynamic data acquisition and data bases development
- Organic molecules and RN behaviour within processes
Spectre ESI-MS du ligand + U(VI)
Spe
ciat
ion
Mass spectrometry : chelating molecules and speciat ionMass spectrometry : chelating molecules and speciat ion
DEN/DANS/Saclay – Department of Physical Chemistry
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µ-Raman spectrometry – SEM
Détecteur électronsecondaire
Echantillon
Détecteur électronrétrodiffusé
Bras retractable
Laser beamLaser beam
Raman diffusionRaman diffusion
� Micrometric particles analysis, study of chemical forms of U compounds� Detection and location by SEM-EDX, transfer to µ-Raman, relocation
µ-RamanMEB
Disque C
� U reference compounds spectra, characteristic Raman bands identification
Spe
ciat
ion
DEN/DANS/Saclay – Department of Physical Chemistry
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• Miniaturization of sample amount• Reduction of reagent and waste volumes• Reduction of contaminations• Reduction of dose rate• Systems can be coupled to spectrometric techniques
Interests of microsystems for DEN
Analytical micro-systems
- Device (a few cm²) with channels(1-100 µm) in which fluids move (pL-µL)
- Fabricated with microtechnologies from microelectronic (prototypes by laser ablation)
- Miniaturisation and integration of analytical steps on these devices : Micro Total Analysis System => µTAS, Lab-on-chip.
10 µm x 10 µm x 1 cm = 1 nL
Min
iatu
rizat
ion
Micro-nebulizer CEA (2 cm * 1 cm)
DEN/DANS/Saclay – Department of Physical Chemistry
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Connexion capillaire (C)
Terminal (T)
Echantillon (S)Leader (L)
Membrane (M)
PPS
PSL
PPT
Détecteur conductimétrique (CD)
Sortie capillaire (O)
IC SC
Example : lanthanides separation by isotachophoresi s for isotopic analysis
Lanthanides separation0.8 µL, 6 ng/element
Polymeric chip design : hot embossing (Université Lyon I, INL).
- Sample is sandwiched between leader and terminal
electrolyte
- Separation by constant current
- Species “reorganized” according to electrophoretic
mobilities
PrinciplePrinciple
B
CC
C
BC
CB B
B
BB
+ -
+ -
A A
A
AAA
B
L
T
BBB
B
B
A
A
A AAA
B
+ -B
B
B
A
AA
A
A
B A
A
A
B
B
BB
A
A
AT
T
L
LC
C
C
C
CA
BBC
C
C
C
C
C
C
CC
CCCC
C
C
C
C
C
C
I
A
C
B
B
B
L
T
Sig
na
l de c
on
du
cti
vit
é
CB
A
Position dans le système
Min
iatu
rizat
ion
DEN/DANS/Saclay – Department of Physical Chemistry
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ITP - ICP-MS coupling
Capteur C4D
0,00
0,10
0,20
0,30
0,40
0,50
0,60
0,70
985 990 995 1000 1005 1010 1015 1020
Temps (s)
Inte
nsité
(u.
a.) IC
PM
S M
C
142Nd
143Nd
144Nd
145Nd
146Nd
148Nd150Nd
150Sm
148Sm
144Sm
147Sm
149Sm
Nd and Sm mass spectrum(ITP-ICPMS MC coupling)
ITP separation Interface ICPMS source
=> Reduction of handled and analysed amounts :
- Sample volume : from 1 mL to 1 µL
- Amount : from µg to ng per lanthanide,
- Effluents : from 1 L to 1 mL.
ITP – ICPMS coupling : same results than in macro system for lanthanides isotope ratio measurements.
⇒ Perspectives : speciation on chip by hyphenation separative techniques – ESIMS and ICPMS
Example : lanthanides separation by isotachophoresi s for isotopic analysis
Min
iatu
rizat
ion
DEN/DANS/Saclay – Department of Physical Chemistry
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Example : Thermal Lens Spectrometry (TLS)
Détecteur CCD
• From the development of « integrable » spectrometry
� Independent of volume sample
� Interferometric detectionindependent of probe intensity
DEN/DRCP/SEAA/LAMM, IMEP-LAHC/INP-Grenoble
1,2
1,4
1,6
1,8
2
0 0,02 0,04 0,06 0,08 0,1 0,12
concentration (mol.l -1)
inte
rfrin
ge
(mm
)
Laser sonde
laserpompepulsé
• To optical integration on microsystem
� optical waveguide embedded by ion-exchange process (n change)
� 2 systems in //, detection basedon phase shift (Young’s double slit)