Radiochemistry and environmental processes · Radiochemistry and environmental processes...
Transcript of Radiochemistry and environmental processes · Radiochemistry and environmental processes...
Christophe Den Auwer
Radiochemistry and environmental processes
Processus Chimiques et Radiochimiques dans l’EnvironnementHydrosphere
German-‐French research for nuclear safety: Chemistry of the f-‐elements, 22-‐23 Février 2012
Transfer and behavior of trace elements
Radioisotope tagging, metabolomics
Bioactinidic chemistry
Chemical and Radiochemical Processes in the Environment Hydrosphere
Interface with the geosphere fluxes
Interface with the biotope toxicology
Aqueous chemistry of trace- and radio- elements
Bioactinidic chemistry XAS HPLC/ICPMS
Biomonitoring Radioisotope Tagging HPLC, NMR µ-imaging
Trace- and radio- elements
ICP-MS radiometry
XAS IR-Tf NMR
PDB 1FCK
molarity
Intermediate domain
Trace and ultra trace domain
... Tagging, Tracer
Inventory, transfer
Radiometry, HPLC-ICPMS
µimaging, XAS, HPLC-ICPMS
XAS, NMR, IR-Tf
Molecular bioactinidic chemistry
10-‐1 10-‐9 10-‐6
Th
Np
Weighable domain
Transuranium chemistry CEA Marcoule, IPN Orsay Np ... Pu Am
U Am RN
(ppb) (ppm)
Structural and spectroscopic probes
Th U
© Elementaire 2005, de l’infiniment petit à l’infiniment grand, LA L / CNRS, IN2P3
Chemical analogues ionic radius RedOx properties Hardness (Pearson) Property of hte valence orbitals ....
Most analogues are system dependant
Important role of the chemical analogues
Inventory and transfer of radionucleides in the environment
Investigation of the consequences of the Tchernobyl accident (April 1986)
Inventory of 137Cs, IRSN
Investigation of the consequences of the nuclear tests from 1945 to 1980
Cumulated dose 1945-‐1980
Fiche IRSN 2008, Les essais atmosphériques d’armes nucléaires : des retombées radioacVves à l’échelle planétaire
Stopping of the atmospheric nuclear tests : USSR, USA = 1962 France = 1974 China = 1980
SimulaVon of the Cs fallout from precipitaVon data of May 1986
Fiche IRSN 2011 : Tchernobyl, 25 après
G. Barci-‐Funel, J. Dalmasso, G. Ardisson, Pollut. Atmos. 121 (1989) 94. G. Barci, J. Dalmasso, G. Ardisson, J. Radioanal. Nucl. Chem. 117 (1987) 337.G. Barci-‐Funel, J. Dalmasso, G. Ardisson, J. Radioanal. Nucl. Chem. 164 (1992) 157. S. Rezzoug, in Laboratoire de Radiochimie, Sciences AnalyVques et Environnement, Université de Nice-‐Sophia AnVpolis, Nice, 2005. M. Schertz, in Laboratoire de Radiochimie, Sciences AnalyVques et Environnement, Université de Nice-‐Sophia AnVpolis, Nice, 2004.
QuesVon : leaching and storage mechanisms in a mountain catchment basin
Amélie Leclercq
« Chalet Vidron » : 1765 m, Massif du Boréon, Mercantour National Parc Area of the drainage basin : 2 km²
Area of the catchment basin : 650 m²
Aurélie Barats
Solid samples (25/09/2009) : – 7 sediments (18 to 23 cm – 7 or 8 slices of 3 cm)
– 2 soils (27 cm – 3 slices of 9 cm)
• Drying : 40 °C • Sifting : 2 mm
Nuclear spectrometry
238,239+240Pu 241Am
137Cs
α γ
U, Th
ICP-Mass spectrometry
Trace nucleides
Sampling area
Anthropogenic 137Cs
1991 Streaming of the lake
depth Vme
Integrated quantities
Depth profile
SchemaVc profile of RN drainage
1986 : Tchernobyl
Streaming of the lake
depth Vme
Depth profile
1991
1951
1962 Last atmospheric nuclear test for USA, UK, USSR
1980 Last atmospheric nuclear test for China
Speciation of radioelements and analogues in natural water
[Eu] = 5.10-5 M ( 10 ppm)
New study on sea water
!
CHESS speciation
pH
IAEA Monaco CEA Marcoule, Bruyères le Châtel
Marine environment is prone to a large array of metal contaminations due to natural phenomena but also anthropogenic activities. Contamination by radionuclides (radioelements) is a possible bioindicateur
Sponges are filtering ancient organisms present in all marine ecosystems.
They can serve as biomonitors for a contamination of the marine environment.
Sponges as biomonitors for a metal pollution of the marine environment
IAEA Monaco
Comparative bioaccumulation of trace elements in Mediterranean marine sponges
- 6 sponge species have been investigated - 8 gamma-radiotracers 110mAg, 241Am, 109Cd, 60Co, 134Cs, 54Mn, 75Se and 65Zn - Uptake and loss kinetics of the bioaccumulation of these trace elements
Acanthella acuta
Massive sponges show high Concentration Factors for all trace elements (x100 / mussels).
Acanthella acuta highly accumulates Ag but does not loose it complexation with a metabolite ?
Role of primary or secondary metabolites ?
Ongoing work with radio and astables nucleides
Bioaccumulation by different sponge species
- Complexation by biomolecules
- Biotransformation ?
- Bioremediation ?
Perspectives : bioaccumulation of anthropogenic radioelements by sponges
First step : Am / Eu analogy
Trace level : transfert and inventory
Complexation : significant metabolite
Co-ligand
U(VI) Th(IV) Np(IV), Np(V) Pu(IV)
skeleton, kidneys
skeleton, liver
skeleton (major.) liver
soluble : skeleton > liver insoluble : liver > skeleton
An “ “
Biomolecule vector
Target organs
Chelating peptide, metobolite
cont
amin
atio
n
Ex : transferrine calmoduline albumine ....
P. W. Durbin, Health Phys. (1975), 29, 495.
Simplified system
Chemistry of the actinides with biological molecules
Peptide : simpler system
Asp
Pro
N C
Protein : complex system
Simplification of the system
His
N C
(P)Ser
Asp
Glu (P)Ser
Asp
Glu
Val
IPN Orsay
0 1 2 3 4 5 6
chir_magfit U193
FT m
agni
tude
k3 !
(k)
R + " (Å)
phosphate
carboxylate
The phosphorylated amino acids : phosphoserine
Coordination ≅ 1 phosphate, 1 monodentate carboxylate, 1bidentate carboxylate, 1 water molecule
2 Oyle at 1.78 Å, σ2 = 0.0034 Å2
2 O(carb + phos) at 2.29 Å, σ2 = 0.0031 Å2
2 O(carb bid) at 2.49 Å, σ2 = 0.0070 Å2
1 P at 3.80 Å, σ2 = 0.0080 Å2
Sequence of the H8V peptide
0 1 2 3 4 5 6
FT a
mpl
itude
k3 !
(k)
R + " (Å)
pH = 5.0
His
N C
(P)Ser
Asp
Glu (P)Ser
Asp
Glu
Val
2 Oyle at 1.78 Å, σ2 = 0.0031 Å2
2.6 O(carb + phos) at 2.30 Å, σ2 = 0.0069 Å2
4.0 O(carb bid) at 2.49 Å, σ2 = 0.0100 Å2
0.4 P at 3.75 Å, σ2 = 0.0020 Å2
P Glu
Asp
Glu
0 1 2 3 4 5 6
FT a
mpl
itude
k3 !
(k)
R + " (Å)
pH = 1.5
pH = 3.0
pH = 5.0
{UO22+} aq
Mainly carboxylates (monodentate) Carboxylate and phosphates
SLRT
EXAFS
2 Oyle at 1.78 Å, σ2 = 0.0031 Å2
2.6 O(carb + phos) at 2.30 Å, σ2 = 0.0069 Å2
4.0 O(carb bid) at 2.49 Å, σ2 = 0.0100 Å2
0.4 P at 3.75 Å, σ2 = 0.0020 Å2
2 Oyle at 1.78 Å, σ2 = 0.0020 Å2
2.9 O(carb + phos) at 2.34 Å, σ2 = 0.0051 Å2
1.4 O(carb bid) at 2.53 Å, σ2 = 0.0053 Å2
0.7 P at 3.80 Å, σ2 = 0.0060 Å2
2 Oyle at 1.78 Å, σ2 = 0.0040 Å2
3.7 O(carb + phos) at 2.35 Å, σ2 = 0.0101 Å2
1.0 O(carb bid) at 2.52 Å, σ2 = 0.0006 Å2
0.8 P at 3.80 Å, σ2 = 0.0060 Å2
Mainly carboxylates (mono + bidentate)
Aims and new directions
Inventory, behavior and transfer of trace elements in the environement - Spacial and chronological distribution, stable and radioactive elements : inventory, balances - Biogeochemical processes : macroscopic fluxes, transfert phenomena - Reactivity in natural medium
Molecular and bioactinidic chemistry - Interaction with biological actors, toxicology - Speciation in natural medium, aqueous chemistry - Molecular chemistry of the actinides, spectroscopy
Marine and environnemental metabollomics - Marine metabolic routes, radioisotope tagging - Marine ecology, contamination - Model biomonitors, isotopes and radioelement interaction
CEA-‐DEN ToxNuc-‐E 2004-‐2007
Acknowledgements
CEA Marcoule E. Ansoborlo (DEN) C. Vidaud (DSV) G. Creff (DSV)
IPN Orsay S. Safi A. Jeanson E. Simoni
Synchrotron SOLEIL /MARS P. L. Solari S. Schultig B. Sitaud
Synchrotron ESRF / FZDR-ROBL C. Hennig A. C. Scheisnost
ICN Nice A. Leclerc H. Michel O. Thomas A. Barat I. Monfardini
CEA Bruyères le Châtel J. Aupiais C. Moulin