# Radionuclide measurements by mass spectrometry and radiometric techniques: differences and complementarities

Hélène Isnard, Valérie Lourenco

► To cite this version:

Hélène Isnard, Valérie Lourenco. Radionuclide measurements by mass spectrometry and radiometric techniques: differences and complementarities. Workshop on the Use of Mass Spectrometry in Radionuclide Metrology, Feb 2023, WEBINAR, France. cea-04037053

HAL Id: cea-04037053

https://cea.hal.science/cea-04037053

Submitted on 20 Mar 2023

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
# Radionuclide measurements by mass spectrometry and radiometric techniques: differences and complementarities

cea

DE LA RECHERCHE À L'INDUSTRIE

ISNARD Hélène

Laboratoire de développement Analytique Nucléaire
Isotopique et Elémentaire (LANIE)

LOURENÇO Valérie

Laboratoire National Henri Becquerel (LNHB-MA)

Direction des Energies, CEA Saclay, ISAS/DRMP/SPC/LANIE
CEA, List, Laboratoire National Henri Becquerel (LNE-LNHB)
- **High precision isotopic and elemental analysis by Mass Spectrometry**

- Fuel samples, Irradiated target,
  - Safeguard samples ...

<figure><img src="image_2.png" /></figure>

<figure><img src="image_3.png" /></figure>

- **Mass Spectrometer** instruments in glove boxes

- 2 TIMS, 2 ICPMS MC, 1 ICPMS Q

<figure><img src="image_4.png" /></figure>

<figure><img src="image_5.png" /></figure>

- **Separative techniques** for purification and coupling with MS

<figure><img src="image_6.png" /></figure>

- **Triple to Double Coincidence Ratio (TDCR)**

- Primary technique based on Liq. Scintillation Counting + a physical model of light emission

Optical chamber

<figure><img src="image_7.png" /></figure>

<figure><img src="image_8.png" /></figure>

<figure><img src="image_9.png" /></figure>

3 photomultipliers

- **4πβ-γ coincidence method**

- Primary technique coupling LSC and HPGe or NaI γ counter (no model needed)

HPGe detector

<figure><img src="image_10.png" /></figure>

- **Other primary techniques**
## Determination of **half-life**

Long-lived
fission products

<table><thead><tr><td>RN</td><td>Half-life</td><td>Spike (DI)</td><td>Ref</td></tr></thead><tbody><tr><td><sup>93</sup>Zr</td><td>1,64 ± 0,06 x 10<sup>6</sup> ans (3,6 %)</td><td><sup>96</sup>Zr</td><td>[1]</td></tr><tr><td><sup>151</sup>Sm *</td><td>96,6 ± 0,6 ans (0,6 %)</td><td>Sm nat</td><td>[2]</td></tr><tr><td><sup>129</sup>I *</td><td>16,14 ± 0,12 x 10<sup>6</sup> ans (0,7 %)</td><td><sup>127</sup>I</td><td>[3]</td></tr><tr><td><sup>166m</sup>Ho *</td><td>Purification only</td><td>-</td><td>[4]</td></tr></tbody></table>

* Metrology for Radioactive Waste Management (EMRP)

3 EURAMET

Supplementary comparisons

## Other collaborations

<table><thead><tr><td>RN</td><td>Goal</td><td>Purpose</td><td>Ref</td></tr></thead><tbody><tr><td><sup>147</sup>Nd</td><td>Absolute gamma-ray emission intensities (neutron flux dosimeter)</td><td>Purification from <sup>147</sup>Pm</td><td>[5]</td></tr></tbody></table>

<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /></figure>

Development and characterisation of
2 reference materials

[1] Cassette P., Chartier F., Isnard H., ..., Bé M.M., Lepy M.C., Tartes I. *Applied Radiation and Isotopes* **68**, 122-130 (2010)

[2] Bé M.M., Isnard H., Cassette, P., Lourenço V., Nonell A., Chartier .. et al. *Radiochimica Acta* **104**, 131-139 (2015)

[3] Garcia-Torano E., Bé M.M., Bobin C., Lourenço V., Isnard H., Chartier F...et al. *Applied Radiation and isotopes*, **140**, 157-162 (2018)

[4] Gueguen F., Isnard H., Kossert K., Nonell A., Chartier F., et al. *Journal of Radioanalytical and Nuclear Chemistry*, **302**, 289-295 (2020)

[5] Kellett M., Bobin C., Isnard H., Lépy M.C., Lourenço V, Vio L. ... et al. *Applied Radiation and Isotopes* **166**, 109349 (2020)
- **Purification step(s)** to isolate the element of interest

- Spectral and non spectral interferences by **mass spectrometry**

- Active radionuclides for **radiometric measurements**

<figure><img src="image_13.png" /></figure>

- State of the art on precise **mass spectrometric** measurements

- **<u>Use of Isotope Dilution</u>**: Choice of spike

- **<u>Multicollector Mass spectrometer</u>**: TIMS or ICPMS MC (complementarities between the two techniques)

- Link between mass and activity

<figure><img src="image_14.png" /></figure>

Activity (Bq = s⁻¹)

$$n = \frac{A \cdot T_{1/2}}{N_A \cdot \ln 2}$$

<figure><img src="image_15.png" /></figure>

Amount of substance (mol)

<figure><img src="image_16.png" /></figure>

Illustration on the determination of ¹⁵¹Sm half life
**Sample:** Irradiated powder of a ¹⁴⁹Sm₂O₃ (95.1%) target irradiated in a french nuclear power plant

- 5.8 mg of Sm₂O₃ powder was irradiated and dissolved in nitric media in French installation

- After irradiation around 400 µg of ¹⁵¹Sm were present

<table><thead><tr><th>Sm</th><th>Mass (µg)</th><th>Eu</th><th>Mass (µg)</th><th>Gd</th><th>Mass (µg)</th></tr></thead><tbody><tr><td>¹⁴⁴Sm</td><td>1.4</td><td></td><td></td><td></td><td></td></tr><tr><td>¹⁴⁷Sm</td><td>4.7</td><td></td><td></td><td></td><td></td></tr><tr><td>¹⁴⁸Sm</td><td>61</td><td></td><td></td><td></td><td></td></tr><tr><td>¹⁴⁹Sm</td><td>907</td><td>-</td><td></td><td></td><td></td></tr><tr><td>¹⁵⁰Sm</td><td>3238</td><td></td><td></td><td></td><td></td></tr><tr><td>¹⁵¹Sm</td><td>402</td><td>¹⁵¹Eu</td><td>10</td><td></td><td></td></tr><tr><td>¹⁵²Sm</td><td>296</td><td>¹⁵²Eu</td><td>0.3</td><td>¹⁵²Gd</td><td>0.2</td></tr><tr><td></td><td></td><td>¹⁵³Eu</td><td>70</td><td></td><td></td></tr><tr><td>¹⁵⁴Sm</td><td>14</td><td>¹⁵⁴Eu</td><td>16</td><td>¹⁵⁴Gd</td><td>5</td></tr><tr><td></td><td></td><td>¹⁵⁵Eu</td><td>5</td><td>¹⁵⁵Gd</td><td>3</td></tr><tr><td></td><td></td><td></td><td></td><td>¹⁵⁶Gd</td><td>2</td></tr><tr><td></td><td></td><td></td><td></td><td>¹⁵⁷Gd</td><td>0.1</td></tr></tbody></table>

<figure><img src="image_17.png" /></figure>

Level of purification different for Mass Spectrometry and radiometry

<figure><img src="image_18.png" /></figure>

Addition of Ho used as a carrier element (no interferences)
<figure><img src="image_19.png" /></figure>

Separation by **High Performance Liquid Chromatography** (HPLC)

Use of HMBA acid (hydroxy methylbutyric acid)

Coupling with Q ICP-MS

<figure><img src="image_20.png" /></figure>

<figure><img src="image_21.png" /></figure>

<figure><img src="image_22.png" /></figure>

<figure><img src="image_23.png" /></figure>

Same chromatographic separation
for purification of Ho and Nd
<figure><img src="image_24.png" /></figure>

## Choice of the **Spike**

Use of **NIST SRM 3147a**: uncertainty 0.15 % at $k=1$

$$C_s = C_{sp} \times \frac{m_{sp}}{m_s} \times \frac{M_s}{M_{sp}} \times \frac{(150)_{sp}}{(150)_s} \times \frac{\left(\frac{152 Sm}{150 Sm}\right)_{sp} - \left(\frac{152 Sm}{150 Sm}\right)_{mix}}{\left(\frac{152 Sm}{150 Sm}\right)_{mix} - \left(\frac{152 Sm}{150 Sm}\right)_s}$$

<figure><img src="image_25.png" /><figcaption>**Table 1:** Comparison of the recommended and measured isotopic ratios for the NIST SRM 3147 certified natural samarium solution.</figcaption></figure>

<table><thead><tr><th></th><th>IUPAC</th><th>u(x) in %<br>(k = 1)</th><th>This work<br>u(x) (k = 1)</th></tr></thead><tbody><tr><td><sup>144</sup>Sm/<sup>150</sup>Sm</td><td>0.416(5)</td><td>1.2%</td><td>0.4194(4)</td></tr><tr><td><sup>147</sup>Sm/<sup>150</sup>Sm</td><td>2.031(13)</td><td>0.6%</td><td>2.037(4)</td></tr><tr><td><sup>148</sup>Sm/<sup>150</sup>Sm</td><td>1.523(7)</td><td>0.5%</td><td>1.526(1)</td></tr><tr><td><sup>149</sup>Sm/<sup>150</sup>Sm</td><td>1.873(5)</td><td>0.3%</td><td>1.874(1)</td></tr><tr><td><sup>152</sup>Sm/<sup>150</sup>Sm</td><td>3.625(11)</td><td>0.3%</td><td>3.614(2)</td></tr><tr><td><sup>154</sup>Sm/<sup>150</sup>Sm</td><td>3.083(20)</td><td>0.7%</td><td>3.068(3)</td></tr></tbody></table>

Determination by **TIMS** using total evaporation method * Fiedler et al. (1995) *IJMS*, **146/147**, 91-97
*Richter et al. (2011) *JAAS*, **26**, 550

<figure><img src="image_26.png" /></figure>

<figure><img src="image_27.png" /></figure>

Minimisation of isotopic fractionation
<figure><img src="image_28.png" /></figure>

<table><thead><tr><th></th><th>Sample concentration<br/>[<sup>151</sup>Sm] (µg g<sup>-1</sup>)</th></tr></thead><tbody><tr><td>Mixture 1</td><td>0.08524(26)</td></tr><tr><td>Mixture 2</td><td>0.08524(26)</td></tr><tr><td>Mixture 3</td><td>0.08516(26)</td></tr><tr><td>Mixture 4</td><td>0.08530(26)</td></tr><tr><td>Mixture 5</td><td>0.08533(26)</td></tr><tr><td>Mixture 6</td><td>0.08527(26)</td></tr><tr><td>Mean</td><td>0.08526</td></tr></tbody></table>

<table><thead><tr><th></th><th>Uncertainty<br/>fractions %</th></tr></thead><tbody><tr><td>C<sub>Sp</sub></td><td>17.52</td></tr><tr><td>m<sub>Sp</sub></td><td>0.03</td></tr><tr><td>m<sub>S</sub></td><td>3.60</td></tr><tr><td>Atomic masses</td><td>–</td></tr><tr><td>(<sup>150</sup>Sm)<sub>S</sub></td><td>8.08</td></tr><tr><td>(<sup>150</sup>Sm)<sub>Sp</sub></td><td>39.91</td></tr><tr><td>(<sup>150</sup>Sm)<sub>Mix</sub></td><td>30.86</td></tr></tbody></table>
<table><caption>**Table 6:** Final results for the activity concentration A, as reported by the participants. The stated uncertainties u are combined standard uncertainties (k = 1).</caption><thead><tr><th>Participant</th><th>A in kBq g<sup>-1</sup></th><th>u in kBq g<sup>-1</sup></th><th>Measurement method</th></tr></thead><tbody><tr><td>PTB</td><td>79.41</td><td>0.59</td><td>CIEMAT/NIST</td></tr><tr><td>PTB</td><td>79.04</td><td>0.56</td><td>TDCR</td></tr><tr><td>PTB</td><td>79.22</td><td>0.41</td><td>Final result</td></tr><tr><td>LNE-LNHB</td><td>77.87</td><td>0.41</td><td>TDCR and final result</td></tr><tr><td>IRMM</td><td>78.5</td><td>0.4</td><td>CIEMAT/NIST</td></tr><tr><td>IRMM</td><td>78.86</td><td>0.40</td><td>TDCR</td></tr><tr><td>IRMM</td><td>78.7</td><td>0.4</td><td>Final result</td></tr><tr><td>POLATOM</td><td>79.51</td><td>0.48</td><td>TDCR and final result</td></tr><tr><td>CMI</td><td>77.9</td><td>0.93</td><td>TDCR and final result</td></tr><tr><td>SMU</td><td>80.247</td><td>0.376</td><td>TDCR and final result</td></tr></tbody></table>

<table><caption>**Table 7:** ¹⁵¹Sm half-life and uncertainty from the literature and this work.</caption><thead><tr><th>Reference</th><th>T<sub>1/2</sub> (a)</th><th>Uncertainty (a)</th></tr></thead><tbody><tr><td>Flynn et al. [19] (1965)</td><td>87</td><td>9</td></tr><tr><td>Reynolds et al. [20] (1968)</td><td>93</td><td>8.6</td></tr><tr><td>Ming He et al. [21] (2009)</td><td>96.6</td><td>2.4</td></tr><tr><td>This work (2015)</td><td>94.6</td><td>0.6</td></tr></tbody></table>

Measurements by liquid scintillation counting (TDCR, CIEMAT/NIST)

<figure><img src="image_29.png" /></figure>

Publication of a **new value for the half-life of ¹⁵¹Sm** with a significantly **reduced uncertainty (0.6%)**

<figure><img src="image_30.png" /></figure>

Resulted in a **new recommended value for the half-life of ¹⁵¹Sm** with a 10-fold **reduced uncertainty (0.6%)** compared to the previous one (6.7 %)
Thanks for your attention

cea

MERCI