TITRE DE LA PRESENTATION

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The use of calix6arene molecules for actinides
analysis in urine an alternative to current
procedures
IRSN- Internal Dosimetry Department Radiochemistry
Laboratory C. Bouvier-Capely, A. Manoury, A.
Legrand, F. Cuenot, F. Rebière
RRMC 2008
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Role of IRSN
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assessment related to nuclear and radiological
risks
Expertise is based on research
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• Contribution to public policies and technical
  support to public authorities
• Services to industry and other organisations

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• LA SEYNE-SUR-MER
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3 major missions

• Research
• Contribution to public policies and technical
  support to public authorities
• Services to industry and other organisations

New research program
Monitoring of internal contamination
New service to industry
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Context internal exposition
Individual monitoring of workers exposed to a
risk of internal contamination
Incorporation ways
Low activity level
in vivo measurements
in vitro measurements
New radiochemical procedures
a, b, g emitters
X, g emitters
U, Pu, Am
Anthroporadiametry
Chemical purification
Routine analysis
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In vitro measurements Current procedures for
actinides analysis in urine
Principle Actinides measurements by a
spectrometry, after mineralization of the sample
and separation of radionuclides with
chromatographic columns

• Main drawback
• lenghty separation long counting times
  time-consuming

Limits the frequency and flexibility of
individual monitoring
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Routine analysis
Low activity level
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Improvement of radiochemical procedures
Aim to propose an alternative to current
procedures for the separation of
actinides in urine
Performance criteria

• selectivity
• quantitativity
• reproductibility

• speed
• easiness

• Scientific processes
• To find new chelating molecules able to
  selectively remove actinides
• from urine sample
• To study the extraction properties of these new
  ligands with respect
• to the actinides U, Pu, Am
• Transposition for an application in
  radiobioassays

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Calixarenes promising ligand
Size of the cavity in fonction of the cation to
be extracted
HOHN
NHOH
HOHN
Choice of chelating groups having a very good
affinity for the cation to be extracted
Calixarene can be soluble in aqueous phase or in
organic phase
LCarbH3
Trishydroxamic-calix6arene (CONHOH)
LHydH3
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Extraction of U, Pu and Am by LCarbH3 and LHydH3
LHydH3
LCarbH3
LHydH3
These calix6arenes have very good affinity for
U, Pu and Am Possibility of separation U/Pu/Am
pH, composition of solution
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Transposition for routine application

• Liquid-liquid extraction technique
• not well suited for routine
  analysis
• not suitable for treating large numbers of urine
  sample
• generates organic effluents that are likely to
  be contaminated

Transposition to chromatographic
techniques immobilization of calix6arenes
molecules on inert solid support
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APPLICATIONS TO RADIOBIOASSAY
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U analysis in urine with URALIX column

• Radiochemical procedure
• development on synthetic solution
• optimisation on urine samples spiked with U
• validation in collaboration with bioassay
  laboratories
• transposition for environmental samples in
  progress

U
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Performances of URALIX column for U analysis in
urine
Percentages of fixation/elution of U on URALIX
column from spiked urine samples and mineralized
(35 samples)
Results of radiotoxicological intercomparison
Procorad 2007
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Actinides analysis in urine by calix6arenes
mineralized Urine (U, Pu, Am) NaNO2
pH 2
HCl
Pu
Pu
U, Am
calix6arene column
pH 5
1) EDTA
Am
Am
2) HCl
U
U
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Advantages of calixarene columns

• Alternative to current procedures
• One type of column to isolate U, Pu and Am

• 2 passages on the column
• no stage of dry evaporation/recovery
• elution media adapted to measurements (a
  spectro, ICP-MS)

The number of steps is reduced Method simple and
rapid
1 day
Duration (calixarene) / 3 days
(classical procedures)
(without measurement)
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Uranium analysis in urine with URALIX
T0 28 H
T0
T0 8 H
T0 24 H
Reflux heating precipitation filtration
drying/calcination pH ajustement
URALIX separation preparation of the source
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Schedule
Analysis of uranium in urine with URALIX

• From now sending URALIX columns to bioassay
• laboratories which are interested to test it for
  uranium
• analysis in urine
• Beginning 2009 start of the sale of URALIX
  columns

Analysis of U, Pu and Am in urine

• Second quarter of 2009 calixarene columns
• should be offered to bioassay laboratories

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Application to environnemental samples
The case of uranium in drinking water
Drinking water Acidified (U) 500ml
U
AQUALIX column
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THANKS
B. Boulet
J. Ambroise
C. Bouvier
A. Legrand
A. Manoury
F. Cuenot
O. Gandois
C. Cossonnet
L. Poriel
J. P. Bonthonneau
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CONTACTS
François REBIERE (33) 1 58 35 80
38 francois.rebiere_at_irsn.fr Céline
BOUVIER-CAPELY (33) 1 58 35 83 44 celine.bouvier_at_i
rsn.fr IRSN/DRPH/SDI/LRC BP 17 92 262
Fontenay-aux-Roses Cedex FRANCE