1. Winter conference on plasma spectrochemistry Sarah BAGHDADI sarah.baghdadi@irsn.fr Ph. advisor: Pr. Gérard COTE UMR 7575 CNRS-ENSCP, Paris Scientific advisor: Céline BOUVIER-CAPELY IRSN/PRP-HOM/SDI/LRC, Fontenay-aux-Roses Amelia Island, January 08 th, 2014 Actinides analysis in body fluids by on-line coupling between calix[6]arene columns and ICP-MS

2. N uclear crisis! A ccident or terrorist attack? H ow analyses are done? A lpha particles S hort pathways D ifficult in-vivo measurement (high LOD) → Excretion analysis Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 2 R adionuclides released into the atmosphere P eople may be contaminated Sheet of paper

3. 7 to 10 days 8 hours Routine protocol: α spectrometry Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 3 T raditional methods Emergency Thesis: ICP-MS CH22 CC44 U, Pu, Am A new approach Dowex TRU spec UTEVA Digested urine Pu U Am Previous studies: α spectrometry/ ICP-MS CH22 CC44 Pu Am U Digested urine 3 days using ICP-MS Digested urine

4. 1- Sample preparation 4- Chromatographic parameters 2- Extraction procedure 3- On-line analysis Outline Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 4

5. 1- Sample preparation 4- Chromatographic parameters 2- Extraction procedure 3- On-line analysis Outline Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 5

6. Column 2 calix[6]arene-based resins available: R = -COOH, ou R = -(C=O)NHOH Aim: 1 single column Adapted pH Available: CH: Pu(IV) extraction at pH=3 CC: U(VI)/Am(III) extraction at pH=5 Choice: CH Extraction pH > 5 to extract simultaneously U, Pu, Am Aim: 1 single column Adapted pH Available: CH: Pu(IV) extraction at pH=3 CC: U(VI)/Am(III) extraction at pH=5 Choice: CH Extraction pH > 5 to extract simultaneously U, Pu, Am  Extraction protocol Pu(IV) CH Pu(IV) CH Am(III) CC or CH Am(III) CC or CH U(VI) CC or CH U(VI) CC or CH Columns Extraction equilibrium m(Ac) + (LH 3 ) m (LH 3-n (Ac) ) m + nH + K eq =(7,22±0,77).10 -5 M (B. BOULET, 2006) Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 6 Extraction efficiency on real urine matrixes  (53±4) % of U is extracted  (91±2) % of Pu is extracted  (88±3) % of Am is extracted Extraction efficiency on real urine matrixes  (53±4) % of U is extracted  (91±2) % of Pu is extracted  (88±3) % of Am is extracted

7. 1- Sample preparation 4- Chromatographic parameters 2- Extraction procedure 3- On-line analysis Outline Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 7

8. ▌ Parameters  Sodium nitrate solution: Good uranium extraction (> 90%)  Uranium 238 Low specific activity  Elution: HNO 3 Efficient for U, Pu, Am Well suited for ICP-MS  Micro-nebulisor ▌ However, it does not model the real matrix No ionic strength effect Co-elution Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 8  Semi-automated- ICP-MS: Agilent 7700x series with the Integrated Sample Injection System On-line analysis

9. Trash 3/ Elution ICP-MS Column 6-port valve 1/ Extraction: uranium solution On-line analysis  Semi-automated- ICP-MS: Agilent 7700x series with the Integrated Sample Injection System 4/ Conditionning (for futher use): acetate buffer 2/ Rinse: NaNO 3 Off-line On-line UU U U U U U U U U U Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 9

10. 1- Column diameter  3 different diameters: 6, 10, 15 mm  Resin: 1 g  Elution flow rate: 1.1 mL/min avec HNO 3 1M  Sodium nitrate solution: 3.4 g/L  Signal improvement: x 30 Uranium 238 Extraction: 85 % Elution: 67 % Diameters Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 10  Semi-automated- ICP-MS: Agilent 7700x series with the Integrated Sample Injection System On-line analysis  Choice: ф=10 mm

11. 0 0.2 0.4 0.6 0.8 1.0 1.2 Peak tailing is reduced as retention time increases  Efficiency vs. rapidity 0.275 mL/min is the best option N = 400 t = 15 min  Efficiency vs. rapidity 0.275 mL/min is the best option N = 400 t = 15 min Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 11 On-line analysis  Semi-automated- ICP-MS: Agilent 7700x series with the Integrated Sample Injection System 2- Effect of the elution fow rate:  Column diameter: 10 mm  Resin: 1 g  Variable flow rate  Sodium nitrate solution 3.4 g/L

12.  Column diameter: 10 mm  Elution: HNO 3 2M flow rate: 0.82 mL/min  Resin: 1 g  Sodium nitrate solution: 3.4 g/L,  238 U (1.2 µg/L=14 mBq/L), 239 Pu (0.317 µg/L=729 Bq/L), 243 Am (0.002 µg/L=14.8 Bq/L)  Co-elution  Am: signal x 30  Pu: signal x 14  Mass separation only Potential interference 238 U 1 H 239 Pu  Co-elution  Am: signal x 30  Pu: signal x 14  Mass separation only Potential interference 238 U 1 H 239 Pu Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 12 On-line analysis

13.  Automated analysis - ICP-MS: Agilent 7700x series Trash 3/ Multi elution ICP-MS Column 6-port valve 4/ Acetate buffer (pH=6) 12-port valve 1/Mineralised urines 2/ and 4/NaNO 3 P 1 Isocratic pump P 2 Quaternary pump A: carrier 1 2 3 4 5 6 Position 1: load Position 2: inject flush V1V1 V2V2 Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 13 On-line analysis

14.  Automation  Theoretical plate theory confirms columns efficiency Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 14  Automated analysis - ICP-MS: Agilent 7700x series On-line analysis ISIS Automated Automated 2 ISIS2

15.  U, Pu, Am are simultaneously extracted on a single column  Extraction  U extraction is urine dependent A synthetic urine is being developped  Elution  Improved elution U, Pu, Am Example: HCl 0.2 M + NH 4 OCl 3.5 g/L Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 15 Conclusions and prospects

16.  Chromatographic parameters  Diameter: 10 mm  Elution flow-rate: 0.275 mL/min  Automated analysis  Parameters confirmed  We need to validate the method on real urine samples with U, Pu, Am Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 16 Conclusions and prospects

17. Many thanks to Céline Bouvier-Capely Gérard Cote Alexandre Legrand, Annabelle Manoury, Aurélie Sylvain, Clément Beyaert, François Rebière Grégory Lefèvre, Céline Fosse Aurélie Ritt, Evelyne Barker, Sylvain Bassot Members of LRC, LECIME, LAME Acknowledgments Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 17

18. Thanks for your attention Any questions ? Winter conference on plasma spectrochemistry-S. Baghdadi-2014/01/08-IRSN 18

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