Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 1

Analysis of a single hot particle by a combination

of non-destructive analytical methods

Erich Hrnecek, Laura Aldave de las Heras, Marek Bielewski

EC Joint Research Centre (JRC)

ITU - Institute for Transuranium Elements

Karlsruhe, Germany

http://itu.jrc.ec.europa.eu

http://www.jrc.ec.europa.eu

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 2

• Introduction – JRC

• Non-destructive analysis of a

radioactive particle

• Dissolution properties after digestion

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 3

Our Structure: 7 Institutes in 5 Member States

IRMM - Geel, Belgium

Institute for Reference Materials and Measurements

ITU - Karlsruhe, Germany

Institute for Transuranium Elements

IE - Petten, The Netherlands

Institute for Energy

IPSC - Ispra, Italy

Institute for the Protection and Security of the Citizen

IES - Ispra, Italy

Institute for Environment and Sustainability

IHCP - Ispra, Italy

Institute for Health and Consumer Protection

IPTS - Seville, Spain

Institute for Prospective Technological Studies

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 4

1963-2008

The mission of ITU is to provide

the scientific foundation for the

protection of the European

citizen against risks associated

with the handling and storage

of highly radioactive elements.

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 5

Radioactive particle

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 6

Radionuclides released to the environment can be in different physico-chemical forms.

This can influence their mobility and bioavailability.

B. Salbu, J.Env.Rad. 96 (2007) 47-53.

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 7

Single radioactive particle

Non-destructive characterization

Dissolution behaviour

in human digestive solutions

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 8

Analytical methods

g-spectrometry – nuclides, activity

SEM – surf. morphology, element composition

m-XRF – elemental distribution

m-XANES – oxidation states

SIMS – surface isotopic distributions & ratios

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 9

Gamma spectrum:

small Cs-137 peak

+ Bremsstrahlung

Cs-137

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 10

SEM

Tescan Vega TS5130 LS SEM

EDX: Ca, Fe

U – inclusions

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 11

Confocal μ-XRF

3D analysis of elemental distribution.

Collects information also from inside of the sample -

from depth up to few hundreds of microns

Multielemental technique.

Nondestructive.

Access to synchrotron facility.

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 12

HASYLAB, Hamburg

monochromator: Si (111)

focusing device: polycapillary lens

10 µm step size

silicon drift detector

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 13

Confocal geometry of measurements

Synchrotron radiation... ...is focused... ...and passes through the sample.

Excited atoms emits

fluorescence radiation...

Properly aligned optics

transmits the radiation only

from a short section of

excited volume.

...in all directions, but...

...only the photons emitted

into the polycapillary solid

angle can reach the

detector.

On its way the atoms are excited.

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 14

Ca matrix of particle

Fe on the surface

Uranium inclusions

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 15

Confocal μ-XANES

X-ray absorption near edge structure

Confocal geometry

Fluorescence mode

U LIII absorption edge

4 Uranium inclusions measured

U oxidation states

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 16

sample absorption edge energy mean oxidation state location of measurement point

UO2 17168.65 (09) 4

U3O8 17170.77 (08) 5.33

sediment point 1 17170.87 (24) 5.40 (15) central part

sediment point 2 17171.85 (29) 6.01 (18) surface layer

sediment point 3 17171.90 (34) 6.04 (21) surface layer

sediment point 4 17171.24 (26) 5.63 (16) central part

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 17

SIMS

Cameca 6f

O2- primary beam

Depleted Uranium

U-236

Weight %

U-234 0.0046 ± 0.0005

U-235 0.312 ± 0.002

U-236 0.057 ± 0.001

U-238 99.627 ± 0.002

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 18

Dissolution

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 19

Compound Mmol/l

Calcium Carbonate 2

Magnesium Carbonate 2.1

Potassium Chloride 9

Sodium Chloride 48

Sodium Lactate 2.2

Citric acid 0.21

Urea 5

Pepsin (1 g/l)

Compound Mmol/l

Calcium Carbonate 2

Magnesium Carbonate 2.1x10-3

Potassium Chloride 9

Sodium Crloride 48

Sodium Lactate 2.2

Citric acid 0.21

Urea 13.3

Pancreatin (2 g/l)

Bovine Ox Gall powder (2 g/l)

Stomach Solution Small Intestine Solution

Physiological Model for the Study of the

Dissolution Characteristics of Environmental Particles

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 20

Stomach (solution 1)

Stomach Compartment

Radioactive Particle

Stomach (solution 2)Stomach Compartment

Intestine Compartment

Intestine (solution 1)

(1 hour, 37°C)(1 hour, 37°C)

+ fresh stomach solution

+ fresh intestine solution

(4 hour, 37°C)

Leaching solutions

Gamma spectrometry

LSC for Sr-90

ICP-MS for Uranium and Tc-99

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 21

Cs-137 [Bq] Cs-137 %

Stomach 1 0.364 ± 0.038 95.2 ± 9.9

Stomach 2 0.019 ± 0.002 4.8 ± 0.6

Intestine < 0.004 < 1

Residual < 0.004 < 1

Cs-137

0.383 Bq in total

in stomach compartment

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 22

Sr-90 [Bq] Sr-90 %

Stomach 1 23300 ± 1200 95.4 ± 6.6

Stomach 2 1036 ± 52 4.2 ± 0.3

Intestine 72 ± 4 0.29 ± 0.02

Residual 5.6 ± 0.4 0.023 ±0.002

Sr-90

24400 Bq in total

in stomach compartment

LSC after separation

with Sr-Spec

10 mg Sr carrier

ICP-MS for recovery

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 23

Uranium [ng] Uranium %

Stomach 1 26.3 ± 0.5 60.0 ± 1.4

Stomach 2 7.1 ± 0.1 16.3 ± 0.4

Intestine 1.24 ± 0.04 2.8 ± 0.1

Residual 9.1 ± 0.2 20.9 ± 0.5

Weight %

U-234 0.0046 ± 0.0002

U-235 0.419 ± 0.008

U-236 0.041 ± 0.001

U-238 99.54 ± 1.74

Uranium

43.6 ng in total

21 % in residual fraction

composition in agreement with SIMS

Tc-99 not detected < 1 pg

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 24

Summary

Non destructive analysis of particle

Ca, Fe major components

U inclusions, more oxidised on surface

Depleted Uranium

Sr-90 major activity, soluble

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 25

Gerald Falkenberg

Mats Eriksson, Maria Betti

Marek Bielewski, Ramon Carlos and many others...

Int. Symp. on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies, 27 03 - 01 04 2011, Monaco 26

Thank you!