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

137Cs : sorption process natCs : core Minor

Correlation between 241Am and 238+240Pu

Am ≈ Pu but different from 137Cs profile

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