Innov Analytiques CETAMA 50ans FC [Mode de compatibilit ] · PPT Détecteur conductimétrique (CD)...

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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


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� New challenges, new needs =>

- need to improve analytical performances, analytical conditions…

- need to develop new methods, new tools

… to anticipate and support DEN programmes

Spectre XPS-Fe2p de l'acier 254SMO

10000

12000

14000

16000

18000

20000

22000

24000

700705710715720725730735

Energie de liaison (eV)

Intensité (cps)

passivation durant 5 jours à l'air

immersion durant 10 jours en eau de mer naturelle

FeIII

Fe0

Gas - liquid - solid – aerosol - surface - interfaceMolecular - elementary - isotopic – speciationRadioactive – non radioactive environments

- Multi-scale approach- Multi-disciplinary approach- Collaboration network


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Research strategy in analytical innovation

BasicPhysical-chemistry

Concepts, R&D,Modelling…

AnalyticalDevelopmentsMethodology

InstrumentationChimiometry

Metrology

ApplicationsNeeds

Nuclear Energy… others by dual

research

- Remote analysis, in situ- Traces and ultra-traces, Isotopy- Speciation- Miniaturisation…

Main concerns of R&D


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� Elementary composition : solids, liquids, gases

� No sample preparation

� Real-time measurement

� Detection limits : 100 ppb to 100 ppm

Laser Laser InducedInduced Plasma Plasma SpectrometrySpectrometry (LIBS)(LIBS)

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10000

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250 255 260 265 270 275 280

spectre optique

plasma

LASER

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250 255 260 265 270 275 2800

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spectre optique

plasmaplasmaplasma

LASERLASER

PRINCIPLE

ValoValo. industrielle : Start. industrielle : Start--up IVEAup IVEA

Rem

ote

Ana

lysi

s

Molten salts for reprocessing studies

Nanopowders caracterisation

Caracterisation of contaminated surfaces in shielded cell

Impurities analysis in Na circuit

Martian rocks analysis– Chem-Cam project (NASA)

Applications : remote and in situ analyses

Contaminated surface detectionAerosols in gas (RCG)Liquid flow analysis (Simul. PF)


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Image de la surface-50

450

950

1450

1950

2450

2950

516.5 517 517.5 518 518.5 519 519.5 520 520.5 521

Wavelength (nm)

Inte

nsity

(a

.u.)

3 meters

5 meters8 meters

12 meters

Mg

Cr

-50

450

950

1450

1950

2450

2950

516.5 517 517.5 518 518.5 519 519.5 520 520.5 521

Wavelength (nm)

Inte

nsity

(a

.u.)

3 meters

5 meters8 meters

12 meters

Mg

Cr

Spectrumposition 1

Spectrum position 2

Resolution between 2 and 10 µm

Experimental

Set-up

Perspectives & outlook : Near-field laser ablation due to needle Ag near the sample surface and in the laser beam.

=> Few dozen nm and quantitative informations.

Microanalysis and elemental mapping (LIBS microprobe)

Laser Laser InducedInduced Plasma Plasma SpectrometrySpectrometry (LIBS)(LIBS)R

emot

e A

naly

sis


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=> Detection of molecules traces in gaseous phase

Time (µs)

Transmitted intensity

In s

itu A

naly

sis

cavité

photodiode

diode laser

PrinciplePrinciple

Laser beam reflected n times in optical cavity formed by 2 mirrors

Decay of transmitted intensity is measured vs time

Rate of intensity loss inside the cavity depends of optical absorbers

Absorption coeff. = concentration X cross section

� Spectral resolution, real time, no sample preparation

� Very high sensitivity (NO2 109 mol / cm3, HF 1 ppb, 1% accuracy at 10-20 ppm)

� Field-portable technique and in-situ measurements

AdvantagesAdvantages

Cavity Ring-Down Spectrometry : CRDS


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� Perspectives : noble gases study, volatile radionuclides …

� 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

Evolution de la concentration de HF mesurée

-5

0

5

10

15

20

25

9:44 10:42 11:39 12:37 13:35 14:32

Temps universel (hh:mm)

ppm

RealReal--time monitoring [time monitoring [ HF] HF]

Coll. Univ. Grenoble

Cavity Ring-Down Spectrometry : CRDSIn

situ

Ana

lysi

s


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Isotopy : interferences resolution by reaction cell in ICPMS

Device under vacuum with a multipôle in which a rea ctive gas is injected :

Separation due to antagonist behaviour between analyte and interfering species

� Resolution in ICPMS of isobaric interferences by ions-molécules reactions in

gaseous phase in a reaction cell.

� Gas selected on thermodynamic et kinetic criteria.

Isot

ope

Ana

lysi

s

ExampleExample : : 9090Sr Sr determinationdetermination in in nuclearnuclear spentspent fuel solutions. fuel solutions.

9090Sr/Sr/9090Zr Zr interferenceinterference suppression suppression with O2 in the reaction cell of ICPMS MC.

Thermodynamic data : Sr+ + O2 � Sr+ et Zr+ + O2 � ZrO+

Kinetic data : Efficiency ~ 82% for Zr

=> O2


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Lentille 1Lentille 2

Lentille 3

HexapôleQuadripôleDétecteur

Cônes

Torche plasmaTorche plasmaLentille 1Lentille 2

Lentille 3QuadripôleDétecteurCônes

Cellule de collision-réaction

O2

Zr+

Sr+

ICP-MS sans cellule de réaction ICP-MS équipé d’une cellule de réaction

Sr

Sr

Résolution de l’interférence

Mesure de Sr possibleRéaction

1249491 95 96

Inte

nsité

/ m

V

500

1000

1500

2000

085 86 88 89 90 92 93

Sr+Zr

87

ZrZr

Zr

Zr

m/z

122123 126 128

Sr

9188

Inte

nsité

/ m

V

500

1000

1500

2000

085 86 87 89 90

Sr

108

ZrO

m/z

106107 110 112

9090Sr Sr determinationdetermination in in nuclearnuclear spentspent fuel solutionsfuel solutionsIs

otop

e A

naly

sis


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1 ‰ relative bias between results obtained:

- by ICPMS MC after interferences separation in the reaction cell and

- by ICPMS MC after chemical separation by liquid chromatography

UOX and MOX samples : 90Sr / 238U measurement by isotope dilution

=> - Removal of the chemical separation step- Analytical time reduction, higher sample throughput- Dose rate reduction- Radioactive waste reduction

Applications : nuclear fuels and « transmutation » samples: separa tion U/Pu (CO 2), Mo/Zr(N2O), Eu/Gd/Sm (O 2), Cs/Ba (N2O)…

Perspectives : Separation Pu/Am, Ru/Pd, Ru/Tc…

9090Sr Sr determinationdetermination in in nuclearnuclear spentspent fuel solutionsfuel solutions

Isot

ope

Ana

lysi

s


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Half-life determination of long-lived RN

DEC/SA3C/LARC with AREVA NC La Hague and CEA LNHB

� New values determination of 79Se emitter β- and 126Sn emitter γ half-lifes(ARI, 2007 ; RCA, 2009 ; JEFF 3.1.1)

� Qualification of neutronic calculation codes, nuclear waste management.

DIFFICULTIES : Interferences in ICPMS, LSC and gamma spectrometry. Very high activity.

AM

mT

×××= 2ln10.02,6 23

Période (s)Masse molaire(g.mol-1)

Activité massique (Bq.g-1)Scintillation liquide 79Se, spectro gamma 126Sn

Concentration massique (g.g-1)ICPMS

AM

mT

×××= 2ln10.02,6 23

Période (s)Masse molaire(g.mol-1)

Activité massique (Bq.g-1)Scintillation liquide 79Se, spectro gamma 126Sn

Concentration massique (g.g-1)ICPMS

1. AREVA La Hague Dissolution of spent fuelSelective extraction of element

PROCEDURE :

Trac

e A

naly

sis


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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)

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coun

ts

Sample A Dil. 100

Sample B Dil. 100 126Sn

666 keV 695 keV

126Sn/126Sb

=> T(79Se) = 3,77 ± 0,19 105 ans=> T(126Sn) = 1,980 ± 0,057 105 ans

Half-life determination of long-lived RN

Trac

e A

naly

sis


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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)


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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


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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


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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)


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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


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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


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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)

TLS conventionnelle

TLS intégrée

• Sample « irradiation »: gradient Tpe, gradient n => thermal lens• Probe laser : phase shift, interference fringes

Application : trace measurement of Np IV in U/Pu for reprocessing

Min

iatu

rizat

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� TRLIF and micro-TRLIF : speciation of actinides, lanthanides…� HPLC (GC) – GDMS coupling : speciation on micro-volumes� SNOM : speciation on nm scale

Other development axesOther development axes

� Sensors�Specific electrode : organic molecules functionalisation (diazonium salt)

Voltammetry. LDD U : 7 10-10 mol L-1 0,2 µg L-1 (UMR Evry)

� Sampling techniques : SPME solid-phase microextraction…

� Speciation

� Nanoparticles characterization

Laser Induced Breakdown Detection Capillary Electrophoresis

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28

18

8

-2

Abs

orba

nce

(mA

U)

35 40 45 5055Mobilité (10 -5 cm 2.V-1.s-1)

10 mM 10 mM HClHClpH = 2pH = 2

γγγγγγγγ--FFee22OO3310,6nm

γγγγγγγγ--FFee22OO338,9nm γγγγγγγγ--FFee22OO33

6,8nm38

28

18

8

-2

Abs

orba

nce

(mA

U)

35 40 45 5055Mobilité (10 -5 cm 2.V-1.s-1)

38

28

18

8

-2

Abs

orba

nce

(mA

U)

35 40 45 5055Mobilité (10 -5 cm 2.V-1.s-1)



γγγγγγγγ--FFee22OO338,9nm γγγγγγγγ--FFee22OO33

6,8nm



γγγγγγγγ--FFee22OO33γγγγγγγγ--FFee22OO33γγγγγγγγ--FFee22OO3310,6nm

γγγγγγγγ--FFee22OO338,9nmγγγγγγγγ--FFee22OO33γγγγγγγγ--FFee22OO33γγγγγγγγ--FFee22OO338,9nm γγγγγγγγ--FFee22OO33

6,8nm

γγγγγγγγ--FFee22OO33γγγγγγγγ--FFee22OO33γγγγγγγγ--FFee22OO336,8nm


Innov Analytiques CETAMA 50ans FC [Mode de compatibilit ] · PPT Détecteur conductimétrique (CD)...

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