Development of an HILIC-ESI-MS method for lanthanide speciation in nuclear fuel treatment processes

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Development of an HILIC-ESI-MS method for

lanthanide speciation in nuclear fuel treatment processes E. Blanchard, Carole Bresson, Anthony Nonell, Benoît Martelat, Fredéric

Chartier

To cite this version:

E. Blanchard, Carole Bresson, Anthony Nonell, Benoît Martelat, Fredéric Chartier. Development of an HILIC-ESI-MS method for lanthanide speciation in nuclear fuel treatment processes. Congrès EWCPS 2017, Feb 2017, Sankt Anton, Austria. �hal-03204936�

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 Two strategies according “Fast HPLC” approach [3-4]:

1)

Reduction the geometrical parameters

of columns (length L

and internal diameter d

_i

) and the

particle size

(d

_p

sub-2-µm)

Sub-2-µm fully porous particles (FPP) introduced in 2004, employed in many application fields

2)

New generation

of column packed with

superficially

porous particles (SPP)

Introduced in 2007

Rapid mass transfer efficiency maintained at high flow-rates

FPP and SPP columns with the same L, d_i and d_p

Expected efficiency (N) 60%, analysis time ÷ 2, V_solvent 45%

with SPP columns in Reversed Phase Liquid Chromatography (RPLC) [5]. However, available stationary phases for HILIC mode are restricted

Analysis time ÷ ~ 1.4 V_solvent ~ 30 % 200 250 300 350 400 450 m/z 0 50 100 0 50 100 0 50 100 0 50 100 R elat iv e Abundan c e 0 50 100 0 50 100 440,0 437,0 243,9 _344,0 230,9 432,0 203,9 257,9 276,9 300,0 317,0 345,0 401,9 395,9 392,9 413,9 368,0 352,0 369,9 364,9 347,0 310,9 _371,9 413,9 300,9 323,9 341,9 318,9 344,0 316,0 293,9 367,9 385,9 252,9 252,9 _295,9 247,9 290,9 297,9 277,9 342,0 244,9 210,9 187,9 359,9 210,9 205,9 270,9 234,9 202,9 _283,9 182,9 -CO₂

Soft ionization technique, allows maintaining the integrity of species

Identification of species

N ÷ ~ 1.70

Allows to obtain the most efficient and fastest separations and to minimize the effluent production.

RT: 0,0 - 60,0 SM: 7B 0 5 10 15 20 25 30 35 40 45 50 55 Time (min) 0 20 40 60 80 100 0 20 40 60 80 100 R e la ti ve Ab u n d a n ce 24,3 26,2 34,4 42,3 16,5 23,2 17,9 28,8 NL: 3,23E6 TIC MS acc-15cm- 0,15mlmin- NdSm-SIM- 5microlitres-18mai NL: 2,99E6 TIC MS acc-10cm-ndsm- sim-10-4m-3microl

 Strategy 1: sub-2-µm FPP

Ethylene Bridged Hybrid (BEH) columns (Waters)

 Selection criteria:

Conditions to achieve the best trade-off between:

- Efficiency of separation N - Analysis time

- Solvent consumption effluent production

Generic methodological approach:

- Lanthanides:

- Polyaminocarboxylic acids: back extraction agents of An/Ln

Formation of Ln complexes: hydrophilic, polar and ionic

Hydrophilic interaction chromatography (HILIC) mode was

selected to separate them [2].

Evelyne BLANCHARD

1,2*

, Carole BRESSON

1 , Anthony NONELL

1 , Benoit MARTELAT

1,2

, Frédéric CHARTIER

3

1

_{CEA Saclay, DEN, DANS, DPC, SEARS, LANIE, Université Paris-Saclay, F-91191 Gif-sur-Yvette, France;}

2

_{Sorbonne Univ, UPMC, F-75005 Paris, France;}

3

_{CEA Saclay, DEN, DANS, DPC, Université Paris-Saclay, F-91191 Gif-sur-Yvette, France}

Introduction

DEVELOPMENT OF AN HILIC-ESI-MS METHOD FOR LANTHANIDE

SPECIATION IN NUCLEAR FUEL TREATMENT PROCESSES

Context:

Research on the sustainable management of radioactive materials and waste has led to dedicated treatment processes based on liquid-liquid

extraction, aiming at selectively recover targeted radionuclides

including lanthanides (Ln) and actinides (An), from current or future

spent fuels.

Radionuclide speciation analysis at various key points is essential to

obtain fundamental data in order to better understand the mechanisms

governing these treatment processes and to assess/improve their performance. LC Separation ESI-MS Structural characterization Quantification

A combination stationary phase/mobile phase was set up:

Amide functionalization 70/30 (v/v) acetonitrile/water [NH₄CH₃COO] = 15 mmol.L-1 0.5 % formic acid EDTA DTPA Sm-EDTA complex 1/ Effic ie ncy RT: 0,0 - 50,0 SM: 7B 0 5 10 15 20 25 30 35 40 45 Time (min) 0 50 100 0 50 100 R e la ti ve Ab u n d a n ce 0 50 100 20,1 21,5 30,4 35,9 _36,0 7,4 7,9 11,3 _13,4 6,9 7,4 10,5 12,2 NL: 4,21E6 TIC MS XBridge-Nd-Sm-SIM-2405 NL: 5,95E6 TIC MS acquity-nd-sm-sim NL: 6,93E6 TIC MS nd-sm-edta- dtpa-0,07mlmin-sim N × ~ 1.80 Analysis time ÷ ~ 2.6 V_solvent ~ 25 % D = 0,30 mL.min-1 [Nd-DTPA+H] -[Sm-DTPA+H]- [Sm-EDTA] -[Nd-EDTA] -[Nd-DTPA+H] -[Sm-DTPA+H] -[Sm-EDTA] -[Nd-EDTA] -D = 0,07 mL.min-1 [Nd-DTPA+H] -[Sm-DTPA+H] -[Sm-EDTA] -[Nd-EDTA] -Column 100 x 1.0 mm, 1.7 µm N ÷ ~ 1.80

Analysis time ~ identical V_solvent 77 %

Extra-column phenomena Column150x 2.1 mm, 3.5 µm

Column 100x 2.1 mm, 1.7 µm

Classical analytical format

FPP Waters BEH 100 × 2.1 mm, 1.7 µm ESI-MS HILIC _HILIC ESI-MS Transposition in glove box

Objectives:

The aim of this work is to develop a Ln speciation analysis method by hydrophilic interaction liquid chromatography (HILIC) [1] coupled to electrospray ionization - mass spectrometry (ESI-MS).

1

Minimization of the effluent production while maintaining

efficient and rapid separations.

2

Structural characterization of lanthanide complexes by ESI-MS.

Results

References

Conclusion/Perspectives

1 Minimization of the effluent production while maintaining efficient and rapid separations

Velocity _Velocity 1/ Effic ie ncy « Fast HPLC » « Fast HPLC »

 Strategy 2: New generation of columns packed with SPP

D = 0,15 mL.min-1

Accucore silica columns (Thermo Fisher Scientific)

D = 0,15 mL.min-1 [Nd-DTPA+H] -[Sm-DTPA+H] -[Sm-EDTA] -[Nd-EDTA] -[Nd-DTPA+H] -[Sm-DTPA+H] -[Sm-EDTA] -[Nd-EDTA] -Column150x 2.1 mm, 2.6 µm Column100x 2.1 mm, 2.6 µm Selected column:

2 Structural characterization of lanthanide complexes by ESI-MS

Conclusion:

- “Fast HPLC” conditions with the FPP Waters BEH column (100 × 2.1 mm, 1.7 µm) allow to obtain the most

efficient and fastest separations and to minimize the effluent production compared to SPP columns.

- The identification of fragmentation pathways of Ln complexes allows:

- Structural characterization speciation information

- To collect data that will be helpful to identify unknown species in real samples

- To develop accurate quantification methods of Ln contained in complexes by HILIC ESI-MS

- To transpose the methodological and instrumental developments in glove box for radioelement speciation analysis

Sm-EDTA-TSQ-Q10,5C-Q21,5Q30,5-scantime0,6-NCE25 #1-100 RT:0,00-1,03 AV:100 NL:1,35E5

T:- c ESI Full ms2 440,000 [200,000-500,000] 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 m/z 0 10 20 30 40 50 60 70 80 90 100 R e la ti ve Ab u n d a n ce 368,09 396,13 398,11 365,08 393,12 324,07 352,10 311,04 342,05 309,02 440,16 268,98 _372,04 296,01 252,96 _386,10 414,17 437,12 243,97 225,03 422,41 445,49 468,45 481,56

Sm-EDTA-40ev-enhanced-HCD-440-l20-tactiv2ms-NCE35 #1-100 RT:0,00-0,56 AV:100 NL:8,47E4

T:ITMS - c ESI sid=40,00 E Full ms2 440,00@hcd35,00 [120,00-750,00]

220 240 260 280 300 320 340 360 380 400 420 440 460 m/z 0 10 20 30 40 50 60 70 80 90 100 R e la ti ve Ab u n d a n ce 413,96 415,95 387,95 385,94 367,96 410,95 369,96 359,96 389,96 357,95 341,97 441,95 395,95 316,94 328,95 436,94 286,94 _299,95 443,97 261,95 _427,96 219,93 228,94

ESI-QqQ-MS (triple quadrupole)

Feature : “In space” tandem mass spectrometry MS/MS (=MS²)

The MS² spectrum of Sm-EDTA, precursor ion 440, Q₁=10, Q₂= 1.5, Q₃=0.5, energy=25

[Sm-EDTA] --CO2+H2O -CO2 -CO -CO2 -CO2 -CO -CO

ESI-LIT-MS (linear ion trap)

Feature: “In time” MSn _(n=2 _{10) for the Collision-Induced Dissociation}

(CID) fragmentation mode

TheMS² spectrum of Sm-EDTA, precursor ion 440, HCD mode with NCE=35% t_activ=2ms, isolation width=20

[Sm-EDTA] --CO₂+H₂O -CO -CO -CO _-CO 2

The MSn_{spectrum of Sm-EDTA, precursor ion 440,}_{CID mode}_{with NCE=35% t}

activ=10ms, isolation width=20

full MS² MS3 MS4 MS5 MS6 NL: 7,96E5 NL: 2,46E5 NL: 7,03E4 NL: 1,38E4 NL: 1,85E3 MS² du 440 MS² du 396 MS² du 368 MS² du 324 MS² du 253 [Sm-EDTA] --CO2+H2O -CO -CO₂

HCD and CID modes

are complementary -CO -CO -CO2 -CH2O +H2O -C2H3N +H2O

[1] L. Beuvier, C. Bresson, A. Nonell, L. Vio, N. Henry, V. Pichon and F. Chartier, “ Simple separation and characterization of lanthanide–polyaminocarboxylic acid complexes by HILIC ESI-MS ”, RSC Adv. 5 (2015) 92858–92868 [2] P. Jandera, “ Stationary and mobile phases in hydrophilic interaction chromatography: a review ”, Analytica Chimica Acta 692 (2011) 1-25

[3] H. Shaaban, T. Górecki, “ Current trends in green chromatography for the analysis of pharmaceutically active compounds in the environmental water compartments ”, Talanta 132 (2015) 739-752 [4] D. Guillarme, J. Ruta, S. Rudaz, J-L. Veuthey, “ New trends in fast and high-resolution liquid chromatography: a critical comparison of existing approaches ”, Anal Bioanal Chem 397 (2010) 1069-1082 [5] J. J. Destefano, S. A. Schuster, J. M. Lawhorrn, J. J. Kirkland, “ Performance characteristics of new superficially porous particles”, Journal of Chromatography A 1258 (2012) 76-83

[6] D. Esteban-Fernandez, A.H. El-Khatib, I. Moraleja, M. M. Gomez-Gomez, M.W. Linscheid, , “ Bridging the gap between molecular and elemental mass spectrometry: Higher energy collisional dissociation (HCD) revealing elemental information”, Anal. Chem. 87 (2015) 1613-1621

Topic of major concern in nuclear applications

Speciation information

 Two mass spectrometers with different analyzers:

Unspecific

fragmentation pathways Specific fragmentation pathways Unspecific fragmentation pathways

- To extend this methodological approach to other treatment processes and the associated samples

 Background

 Composition of model samples

[Sm-EDTA]

-in ESI(-)

According the technologies of the instruments, elemental and molecular information during the same analysis can be obtained [6].

Structural characterization

Limited by “1/3 rule”

Their identification of fragmentation pathways of Ln complexes allows:

- Structural characterization speciation information

- To collect data that will be helpful to identify unknown species in real samples

Perspectives:

19-24 February 2017

D = 0,15 mL.min-1 TSQ QuantumTM (ThermoFisher Scientific) LTQ VelosPro (ThermoFisher Scientific) CID mode HCD mode

Higher Energy Collision Induced Dissociation (HCD) fragmentation mode

*evelyne.blanchard@cea.fr

Acknowledgments:

- The authors gratefully acknowledge the DEN/DISN/PAREC program from the CEA, for its financial support. Fragment mass

The best performances obtained with a FPP column regarding SPP column could be explained by the HILIC mode, involving different