development of a simplified soft-donor technique for

1

Development of a Simplified Soft-Donor

Technique for Trivalent Actinide-

Lanthanide Separations

A thesis submitted to the University of Manchester for the degree of Doctor

of Philosophy in the Faculty of Engineering and Physical Sciences

2015

Madeleine Hilton Langford Paden

School of Chemistry

2

List of Tables

List of Figures

Abstract

Declaration

Copyright Statement

Acknowledgements

List of Symbols amp Units

List of Abbreviations amp Acronyms

Amino Acid Abbreviations

1 Introduction

11 The Actinides and Lanthanides

111 Background

112 Sources of the Actinides and Lanthanides

113 Properties of the 4f Elements


115 Relativistic Effects

116 Lanthanide and Actinide Contraction

117 Co-ordination Chemistry of the Lanthanides and

Actinides in Solution

1171 Hydrolysis

1172 Monodentate Ligands

1173 Chelates and Macrocycles

12 Analytical Methods

121 NMR Spectroscopy

122 Luminescence Spectroscopy

1221 Fluorescence and Phosphorescence

1222 Lanthanide Luminescence

1223 Actinide Luminescence

1224 Sensitised Luminescence and The Antennae

Effect

1225 Russell-Saunders Coupling

1226 Quenching

1227 Quenching in Lanthanides and Actinides

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14

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48

3

1228 Suitable Solvents for Luminescent Complexes

13 Nuclear Theory

131 Nuclear Power

132 The Nuclear Fuel Cycle

133 Spent Nuclear Fuel and Reprocessing

134 Solvent Extraction

1341 PUREX

1342 TRUEX

1343 DIAMEX

1344 SANEX

1345 iSANEX

1346 GANEX

1347 TRPO

1348 LUCA

1349 EXAm

137 TALSPEAK

1371 The Process

138 Reprocessing Summary

14 Project Objectives and Thesis Outline

References

2 Complexation Studies of Ln amp An with DTPA and Buffers

under TALSPEAK Conditions

21 Introduction to An-DTPA and Ln-DTPA Complexes

211 Stability of Ln-DTPA and An-DTPA Complexes

212 Co-ordination Chemistry of Ln-DTPA and An-DTPA

Complexes

22 Ln-DTPA Complexation Studies

221 1H NMR Studies of Ln-DTPA

222 Luminescence Studies of Ln-DTPA

23 An-DTPA Complexation Studies

231 1H NMR Studies of An-DTPA

232 Luminescence Studies of An-DTPA

50

51

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4

24 Introduction to Buffer Interaction with Ln3+

and Ln-DTPA

Complexes

241 Interaction of Lactate with Ln3+

and Ln-DTPA

Complexes

242 Interaction of Amino Acids with Ln3+

and Ln-DTPA

Complexes

25 Studies on Buffer Interaction with M3+

and [M(DTPA)]2-

251 1HNMR Studies on Buffer Interactions

252 Luminescence Studies on Buffer Interactions

2521 Sensitisation Tests

2522 Aqueous Phase Lanthanide Studies without

Na5DTPA

2523 Aqueous Phase Lanthanide Studies with

Na5DTPA

2524 Aqueous Phase Actinide Studies with

Na5DTPA

253 Radiolysis Studies on Amino Acid Buffered Systems

2531 Previous Studies at the INL

2532 Irradiation Studies using Amino Acid Buffers

254 Buffer Interaction Summary

References

3 Solvent Extraction and Optimisation Studies with Amino Acid

Buffers

31 Previous Work at INL

311 L-alanine Studies

3111 pH Studies on L-alanine

3112 Concentration Effects

3113 Studies at pH 2

312 Other Amino Acids

32 L-alanine System Optimisation at pH 2

321 [Na5DTPA] Dependence (EuAm)

322 [HDEHP] Dependence (EuAm)

323 L-alanine Optimisation Summary

33 Other Amino Acid Studies

90

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119

5

331 Initial Tests with Other Amino Acids

332 Studies with L-Histidine

34 Summary of Separations with Amino Acid Buffers

References

4 Studies using L-Glutathione as a Buffer in a TALSPEAK

System

41 Solvent Extraction and Separation using GSH

411 [L-Glutathione] and pH Dependence

4111 [GSH] Dependence without Na5DTPA

4112 [GSH] and pH Dependence with

Na5DTPA

412 [Na5DTPA] Dependence at pH 4

413 [HDEHP] Dependence at pH 4

42 Luminescence Studies using GSH with Eu3+

421 [GSH] and pH Dependence without Na5DTPA

4211 Aqueous Phase Studies

4212 Extraction Studies

422 [GSH] and pH Dependence with Na5DTPA







43 Radiolysis Studies using GSH at pH 4



44 Luminescence Studies using GSH with Dy3+

441 Dy3+

Complexation Studies

442 pH Dependence Studies

45 Luminescence Studies using GSH with Mixed Ln3+

Systems at pH 4

451 Complexation Studies


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6

46 ICP-MS Studies with GSH

47 1H NMR Studies on GSH Systems

48 Summary and Conclusion of Glutathione Work

References

5 Modified DTPA Ligands as Combined Buffers and Soft Donors

in a TALSPEAK System

51 Ligand Synthesis

52 Luminescence Studies on Ligand Systems at pH 2 3 and 4



53 Radiolysis Studies on Ligand Systems at pH 2



54 Separation Work on Ligand Systems

541 AmEu Separation in Ligand Systems

542 Ln Separation in Ligand Systems

55 Summary and Conclusion of Modified DTPA Ligand

Work

References

6 Summary Conclusions and Future Work

61 Summary amp Conclusions

62 Future Work

References

7 Experimental Section

71 Chemicals and Reagents

711 Handling Radioisotopes at INL

72 Complexation studies of Ln3+

amp An3+

with amino acids in

TALSPEAK systems

721 Preparation of samples for luminescence studies

7211 Stock solutions

7212 Preparation of aqueous samples

7213 Preparation of extracted samples

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7

722 Radiolysis of samples

7221 Preparation of Fricke solution

7222 Calculating dose rates

73 Solvent extraction and separation studies using amino

acids and glutathione at INL

731 Preparation of samples

7311 Stock solutions for amino acid studies

7312 [Na5DTPA] dependence SX samples for

amino acid studies

7313 [HDEHP] dependence SX samples for

amino acid studies

7314 Other amino acid SX samples for amino

acid studies

7315 Stock solutions for glutathione studies

7316 [GSH] dependence SX samples without

Na5DTPA

7317 [GSH] and pH dependence SX samples

with Na5DTPA


GSH studies


amino acid studies

732 Gamma counting

733 ICP-MS

74 Luminescence studies and solvent extraction using

glutathione at UoM

741 Preparation of luminescence samples

7411 Stock solutions for GSH studies



742 Radiolysis of GSH samples

74 Modified DTPA Ligands

751 Synthesis of modified DTPA ligands

752 Characterisation of modified DTPA ligands by

MALDI-MS

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209

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210

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210

8


NMR spectroscopy

7531 1H NMR Spectroscopy

7532 13

C NMR Spectroscopy


elemental analysis

755 Luminescence studies with modified DTPA

ligands




7554 Radiolysis of ligand samples

76 Instruments

761 FTS MODEL 812 System 60

Co Irradiator

762 Edinburgh Instrument FP920 Phosphorescence

Lifetime Spectrometer

763 Packard Cobra II Gamma Counter

764 Bruker UltrashieldTM

400 NMR Spectrometer

References

Appendices

Appendix 1 - Emission spectra for [GSH] pH dependence

studies with DTPA in H2O

Appendix 2 - SFLnAm for varying GSH concentration over a

pH range of 2-4 with 005 M Na5DTPA after

extraction with 02 M HDEHP in dodecane

Appendix 3 - Natural pH values for modified DTPA ligands

(005 M) with Eu(NO3)3 (1 mM)

Appendix 4 - APPENDIX 4 - Emission spectra for Eu(NO3)3

with modified DTPA ligands in H2O

Appendix 5 - Emission spectra for radiolysis studies on

Eu(NO3)3 in H2O with DTPA-di(amino acid)

ligands

Appendix 6 - MALDI-MS spectrum for DTPA-(AlaOMe)2

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217

218

218

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220

222

223

224

226

228

9

Appendix 7 - 1H NMR spectrum for DTPA-(AlaOMe)2

Appendix 8 - 1H NMR spectrum for GSH

Appendix 8a - 1H NMR spectrum for Eu(NO3)3 + GSH

Total Word Count 50439

229

230

231

10

LIST OF TABLES

Table 11 Electronic properties of the lanthanides

Table 12 Electronic properties of the actinides

Table 13 Available oxidation states of the actinides and colours of

ions in solution where applicable

Table 14 Luminescence of lanthanide ions

Table 15 Luminescence of actinide ions

Table 16 Approximate compositions of SNF in Light Water

Reactors (LWR)

Table 21 Luminescence lifetimes and q values for Eu3+

with amino

acidslactate

Table 22 Luminescence lifetimes and q values for [Eu(DTPA)]2-

with amino acidslactate

Table 23 Separation factors for Eu3+

Am3+

in the presence of L-

alanine at 05 M under TALSPEAK conditions when subjected

to different doses of γ-radiation

Table 24 Luminescence lifetimes for aqueous and organic phases for

[Eu(DTPA)]2-

systems before and after irradiation at pH 36



Table 31 Distribution ratios and separation factors for a number of

L-alanine buffered TALSPEAK systems as pH and buffer

concentration are varied compared to a traditional lactic acid

system


amino acid buffered TALSPEAK systems

Table 33 Separation factors for L-alanine optimisation studies

Table 34 DAm values for L-alanine optimisation studies

Table 35 Separation factors and DAmEu values for traditional

TALSPEAK systems with different buffers at varying pH

values

Table 41 Eu3+

Am3+

distribution and separation for [GSH]

dependence with 005 M Na5DTPA at pH 4

11

Table 42 Eu3+

Am3+

distribution and separation for [Na5DTPA]

dependence with 05 M GSH buffer at pH 4

Table 43 Eu3+

Am3+

distribution and separation for [HDEHP]

dependence with 03 M Na5DTPA and 05 M GSH buffer at

pH 4

Table 44 Eu3+

Am3+



pH 4


with GSH at

pHD 4

Table 46 J=1J=2 peak ratios and t-test results for Eu-DTPA at pD

2-4 over a GSH concentration range of 01-05 M following

excitation at 397 nm

Table 47 Luminescence lifetimes and q values for Eu-DTPA at pH

2-4 over a GSH concentration range of 01-05 M

Table 48 J=1J=2 peak ratios and t-test results for Eu-DTPA at pH

2-4 as [GSH] is varied

Table 49 J=1J=2 peak ratios and t-test results for Eu-DTPA with

05 M GSH in D2OH2O at pDpH 4 over a Na5DTPA

concentration range of 005-06 M

Table 410 Luminescence lifetimes and q values for Eu-DTPA with

05 M GSH at pH 4 over a Na5DTPA concentration range of

005-06 M following excitation at 397 nm

Table 411 J=1J=2 peak ratios and t-test results for Eu3+

in the

aqueous phase with 05 M GSH at pH 4 as [Na5DTPA] is

varied after extraction with 02 M HDEHP


in the

aqueous phase with 05 M GSH and 03 M Na5DTPA at pH 4

as [HDEHP] is varied after extraction



concentration range of 01-06 M after irradiation with 7 kGy

γ-radiation

12



01-06 M after irradiation with 7 kGy γ-radiation





in the

aqueous phase with 05 M GSH and at pH 4 as [Na5DTPA] is

varied after extraction with 02 M HDEHP in dodecane from

an aqueous phase irradiated at 7 kGy γ ndashradiation

Table 416 Luminescence lifetimes for lanthanide samples at pH 4


and Tb3+

samples at pH 4

Table 418 Luminescence lifetimes for aqueous phases before

extraction over a pH range of 2-4


and Tb3+

samples before extraction over a pH range of 2-4

Table 420 SFLnAm for varying GSH concentration over a pH range

of 2-4 with 005 M Na5DTPA after extraction with 02 M

HDEHP in dodecane

Table 51 J=1J=2 peak ratios and t-test results for Eu- DTPA-

bis(amino ester) complexes at pD 2-4

Table 52 Luminescence lifetimes and q values for Eu-DTPA-

bis(amino ester) complexes at pD 2-4 recorded at the emission

maximum (617 nm) following 397 nm excitation

Table 53 J=1J=2 peak ratios and t-test results for organic phases

after extraction after Eu3+

extraction aqueous phases

containing DTPA-bis(amino ester) ligands (50 mM) at pH 2-4

Table 54 J=1J=2 peak ratios and t-test results for Eu-DTPA-

bis(amino ester) complexes at pD 2 after irradiation with 7

kGy γ-radiation


bis(amino ester) complexes at pD 2-4 after irradiation with 7

kGy γ-radiation

13

Table 56 J=1J=2 peak ratios and t-test results for the organic phases

after Eu3+

extraction from aqueous phases containing DTPA-

bis(amino ester) ligands (50 mM) at pH 2 one of which had

been irradiated with 7 kGy γ-radiation

Table 57 Luminescence lifetimes and q values for the organic

phases after Eu3+

extraction from aqueous phases containing

DTPA-bis(amino ester) ligands (50 mM) at pH 2 one of which

had been irradiated with 7 kGy γ-radiation

Table 71 Dose rates received at each sample position in the 60

Co

irradiator at DCF

Table 72 Elemental analysis results for modified DTPA ligands P =

predicted proportion present () A = actual proportion

present ()

Table 73 Emission and excitation wavelengths for Ln3+

ions

14

LIST OF FIGURES

Figure 11 Jablonski diagram showing fluorescence and

phosphorescence

Figure 12 Energy transfer pathway for sensitised luminescence of

Ln3+

complexes

Figure 13 Energy level diagram showing the ground and excited

states of a selection of lanthanides and vibrational oscillators

Figure 14 The energy gaps between the lowest emissive states and

ground states of a selection of lanthanides and actinides

Figure 15 Chain reaction generated by fission of 235

U into 92

Kr and

141

Ba

Figure 16 The Nuclear Fuel Cycle

Figure 17 Chemical structure of TBP (Tri-nbutyl phosphate)

Figure 18 PUREX flow diagram

Figure 19 Chemical structure of CMPO (NN-diisobutyl-2-

(octyl(phenyl)phosphoryl)acetamide)

Figure 110 TRUEX flow diagram

Figure 111 Chemical structure of DMDBTDMA

Figure 112 Chemical structure of DMDOHEMA

Figure 113 Example DIAMEX flow diagram

Figure 114 General chemical structure of BTPs

Figure 115 Chemical structure of TODGA

Figure 116 Chemical structure of HEDTA

Figure 117 SANEX flow diagram for TODGA process

Figure 118 General chemical structure of BTBPs

Figure 119 Chemical structure of CyMe4-BTBP

Figure 120 Chemical structure of CyMe4-BTPhen

Figure 121 GANEX flow diagram

Figure 122 Chemical structure of TRPO

Figure 123 Chemical structure of CYANEX 301

Figure 124 Chemical structure of TTHA

Figure 125 TRPO flow diagram using TTHA

Figure 126 TRPO flow diagram using HNO3 and oxalic acid

Figure 127 LUCA flow diagram

15

Figure 128 Chemical structure of TEDGA

Figure 129 Chemical structure of DTPA

Figure 130 Chemical structure of HDEHP

Figure 131 Chemical structure of HEH[ϕP]

Figure 132 Chemical structure of lactic acid pKa = 386

Figure 133 The solvent extraction process used in TALSPEAK Step

1 Binding of DTPA to M3+

in the aqueous phase at pH 36

buffered by lactic acid Step 2 Selective extraction of Ln3+

into the organic phase by HDEHP from the aqueous phase due

to preferential binding of DTPA to MA3+

Figure 134 Effect of Na5DTPA concentration on distribution ratios

of MA3+

and Ln3+

in TALSPEAK process using 1 M lactate

buffer and 03 M HDEHP in DIPB extractant

Figure 135 TALSPEAK flow diagram

Figure 21 XAS molecular structure of Gd(III)-DTPA

Figure 22 Chemical structure of [Eu(DTPA)]2-

Figure 23 1H NMR spectrum of [Eu(DTPA)]

2- in D2O at 278 K at

pD = 36

Figure 24 1H NMR spectra of DTPA in D2O at 278 K at varying pD

a) pD 7 [DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]

Figure 25 Emission spectrum of Eu3+

(aq) and [Eu(DTPA)]2-

in D2O

at pD 36

Figure 26 1H NMR spectrum for [Am(DTPA)xH2O]

2- in 41 vv

MeODD2O with NaOD over a temperature range at pH 3

Figure 27 Emission spectrum of Cm3+

and [Cm(DTPA)]2-

in

perchloric acid at pH 3 by direct excitation with a NdYAG

pumped dye laser at 3966 nm

Figure 28 Emission spectrum of Eu-lactate as a function of lactate

concentration

Figure 29 Co-ordination mode of lactate to Eu3+

Figure 210 Chemical structures of L-alanine (top) glycine (bottom

left) and L-serine (bottom right)

Figure 211 1H NMR spectrum of Eu(NO3)3xH2O (10 mM) with L-

alanine in D2O at 278 K

16

Figure 212 1H NMR spectrum of L-alanine in D2O at 278 K


2- (10 mM) with L-

alanine (1 M) in D2O at 278 K

Figure 214 Emission spectra of [Tb(DTPA)]2-

in D2O at pD 3 with

and without the presence of L-phenylalanine (05 M) excited at

250 nm and 379 nm Excitation spectrum of [Tb(DTPA)]2-

in

D2O at pD 3 with L-phenylalanine (05 M) at 545 nm

Figure 215 Chemical structure of L-phenylalanine

Figure 216 Emission spectra of Eu(NO3)3 in D2O at pD 36 with and

without the presence of amino acidslactate (1 M) excited at

395 nm at 298 K

Figure 217 Emission spectra of Eu-DTPA in D2O at pD 36 with and


395 nm

Figure 218 Emission spectrum of [Cm(DTPA)]2-

in H2O with and

without L-alanine (25 mM) at pH 3 by direct excitation at 396

nm

Figure 219 Graph illustrating the rates of reaction of the middotOH radical

with L-alanine compared to lactic acid and the lactate ion

Figure 220 Distribution ratios for Ln3+

and Am3+

in the presence of

L-alanine at 05 M pH 2 at different doses of γ-radiation

Figure 221 Emission spectra of Eu3+

in D2O at pD 36 with and

without the presence of amino acidslactate excited at 395 nm

before 5 kGy γ-irradiation




after 5 kGy γ-irradiation

Figure 31 The effect of pH on an L-alanine-buffered TALSPEAK

system

Figure 32 Distribution ratios of Ln3+

Y3+

in a TALSPEAK system 1

mM LnY3+

1 M lactate 005 M DTPA pH 7 extracted using

05 M HDEHP in 14-DIPB

Figure 33 The effect of buffer concentration on an L-alanine-

buffered TALSPEAK system

17

Figure 34 Chemical structures of L-arginine (top) L-histidine

(bottom left) and L-methionine (bottom right)

Figure 35 DTPA speciation as a function of pH modelled using

HySS sofware using literature pKa values

Figure 36 [Na5DTPA] dependence of L-alanine system (05 M) at

pH 2

Figure 37 Eu3+

Am3+

separation for [Na5DTPA] dependence of L-

alanine system (05 M) at pH 2

Figure 38 Eu3+

Am3+

separation for [HDEHP] dependence of L-

alanine system (05 M) at pH 2 using 02 M Na5DTPA

Figure 39 Eu3+

Am3+



Figure 310 Eu3+

Am3+



Figure 311 Distribution ratios of La3+

-Ho3+

and Am3+

with 05 M L-

histidine buffer at pH 2 and pH 3

Figure 41 Molecular structures of eisenin (top) and norophthalmic

acid (bottom)

Figure 42 Molecular structures of biotinvitamin B7 (top) and folic

acid vitamin B9 (bottom)

Figure 43 Molecular structure of L-glutathione (reduced form)

Figure 44 Eu3+

Am3+

distribution for [GSH] dependence with 005

M Na5DTPA at pH 2 extracted using 02 M HDEHP in

dodecane Results were averaged from 3 repeat tests

Figure 45 Eu3+

Am3+




Figure 46 Eu3+

Am3+


M Na5DTPA at pH 4 Results were averaged from 3 repeat

tests

Figure 47 GSH speciation as a function of pH modelled using

HySS software using literature pKa values

Figure 48 H2GSH- species dominant in solution at pH 4

18

Figure 49 A ternary Nd DO3A-pyrazine amine carboxylate complex

reported by Faulkner at al (left) and anticipated bidentate

chelation of GSH with Am-DTPA at pH 4 (right)

Figure 410 Eu3+

and Am3+

distribution for [Na5DTPA] dependence

with 05 M GSH buffer at pH 4 curves fitted as polynominal

order 2 for both Am3+

and Eu3+

Results were averaged from 3

repeat tests

Figure 411 Eu3+

and Am3+

distribution for [HDEHP] dependence

with 03 M Na5DTPA and 05 M GSH buffer at pH 4 curve

for Eu3+

fitted as polynominal order 2 linear correlation for

Am3+

Results were averaged from 3 repeat tests

Figure 412 Eu3+

and Am3+


with 04 M Na5DTPA and 05 M GSH buffer at pH 4 linear

correlation for both Am3+

and Eu3+

Results were averaged

from 3 repeat tests

Figure 413 Corrected emission spectra of Eu(NO3)3 (1 mM)

Eu(NO3)3 with GSH (05 M) and Eu(NO3)3 with Na5DTPA

(005 M) in H2O following excitation at 397 nm

Figure 414 Emission spectra of Eu(NO3)3 in H2O at pH 4 over a

GSH concentration range of 01 ndash 05 M following excitation

at 397 nm

Figure 415 Emission spectra of Eu(NO3)3 in D2O at pH 4 over a


at 397 nm

Figure 416 Emission spectra of aqueous and organic phases after

Eu3+

extraction at pH 4 using a GSH concentration range of

01 ndash 05 M following excitation at 397 nm


in D2O at pD 2 with 005 M

Na5DTPA over a GSH concentration range of 01 ndash 05 M

following excitation at 397 nm





19





Figure 420 Emission spectra of aqueous phases after Eu3+

extraction

at pH 2-4 over a GSH concentration range of 01-05 M


Figure 421 Emission spectra of organic phases after Eu3+

extraction



Figure 422 Emission spectra of Eu(NO3)3 in D2O at pD 4 with 05

M GSH over a Na5DTPA concentration range of 005 ndash 06 M


Figure 423 Emission spectra of Eu(NO3)3 in H2O at pH 4 with 05




Eu3+

extraction with 05 M GSH at pH 4 over a Na5DTPA

concentration range of 005-06 M following excitation at 397

nm


extraction

with 05 M GSH and 03 M Na5DTPA at pH 4 over an

HDEHP concentration range of 02-10 M following



extraction






after irradiation with 7 kGy γ-radiation following excitation at

397 nm


Eu3+

extraction from irradiated aqueous phase at pH 4

containing 05 M GSH over a Na5DTPA concentration range

of 01-06 M

20

Figure 429 Emission spectra of Dy(NO3)3 Dy-DTPA and Dy(NO3)3

with GSH in H2O following excitation at 352 nm Note that

the tail of ligand emission can be seen in the Dy DTPA and

Dy GSH solutions at shorter wavelengths

Figure 430 Emission spectra of aqueous and organic phases of

Dy(NO3)3 Dy-DTPA and Dy(NO3)3 with GSH after extraction

with 10 M HDEHP following excitation at 352 nm



with 10 M HDEHP following 352 nm excitation

Figure 432 Emission spectra of Ln(NO3)3 (1 mM EuTbSm3+

10

mM Dy3+

) in H2O at pH 4 following direct excitation (405 nm

for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)


10

mM Dy3+

) with GSH (05 M) at pH 4 in H2O following direct

excitation (405 nm for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

Figure 434 Emission spectra of Ln-DTPA (1 mM EuTbSm3+

10

mM Dy3+

005 M Na5DTPA) in H2O at pH 4 following direct


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+

) with GSH (05 M) and Na5DTPA (005 M)

following direct excitation (405 nm for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

Figure 436 Emission spectra of aqueous and organic phases of Ln3+

with 05 M GSH and 005 M Na5DTPA after extraction with

10 M HDEHP at pH 2 following direct excitation (405 nm for

Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

21




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

Figure 439 DLn for varying GSH concentration at pH 2 with 005 M

Na5DTPA after extraction with 02 M HDEHP in dodecane



Figure 441 1H NMR spectra for GSH in D2O under a range of

conditions at 298 K a) GSH b) GSH after irradiation with 7

kGy γ-radiation c) Eu(NO3)3 with GSH d) GSH with

Na5DTPA e) Eu-DTPA with GSH

Figure 442 1H

1NMR proton assignments for GSH (top) and γ-Glu-

Cys (bottom)

Figure 51 General structure of DTPA-amino acid ligands

Figure 52 Emission spectra of Eu(NO3)3 with DTPA-bis(amino

ester) ligands in D2O at pD 2 following excitation at 397 nm






extraction

from an aqueous phase containing DTPA-bis(amino ester)

ligands (50 mM) at pH 2 following excitation at 397 nm

Figure 56 Emission spectra of aqueous and organic phases after Eu3+

extraction from an aqueous phase containing DTPA-bis(amino

ester) ligands (50 mM) at pH 2 following excitation at 397

nm




nm

22




nm

Figure 59 Emission spectra of Eu(NO3)3 in D2O with DTPA-

bis(amino ester) ligands (50 mM) at pH 2 after irradiation

with 7 kGy γ- radiation and following excitation at 397 nm


Eu3+

extraction from an irradiated (7 kGy γ-radiation) aqueous

phase containing DTPA-bis(amino ester) ligands (50 mM) at

pH 2 following excitation at 397 nm

Figure 511 Separation factors and distribution ratios for Eu3+

Am3+

using DTPA-(ArgOMe)2 (005 M) at pH 1-2 extracted using

HDEHP (02 M) in kerosene


Am3+

using DTPA-(SerOEt)2 (005 M) at pH 1-2 extracted using



Am3+

using DTPA-(HisOMe)2 (005 M) at pH 1-2 extracted using



using DTPA-(ArgOMe)2

(005 M) at pH 1-2 extracted using HDEHP (02 M) in

kerosene


using DTPA-(SerOEt)2 (005

M) at pH 1-2 extracted using HDEHP (02 M) in kerosene


using DTPA-(HisOMe)2


kerosene

Figure 61 Chemical structures of amino acids

Figure 71 1H NMR proton assignments for DTPA-(AlaOMe)2

Figure 72 1H NMR proton assignments for DTPA-(ArgOMe)2

Figure 73 1H NMR proton assignments for DTPA-(SerOEt)2

Figure 74 1H NMR proton assignments for DTPA-(HisOMe)2

Figure 75 13

C NMR carbon assignments for DTPA-(AlaOMe)2

Figure 76 13

C NMR carbon assignments for DTPA-(ArgOMe)2

23

Figure 77 13

C NMR carbon assignments for DTPA-(SerOEt)2

Figure 78 13

C NMR carbon assignments for DTPA-(HisOMe)2

Figure 79 60

Co Irradiator at DCF (left) sample holder (top right)

and sample holder inside the irradiator (bottom right)

24

ABSTRACT

The University of Manchester


PhD

Development of a Simplified Soft-Donor Technique for Trivalent Actinide-Lanthanide

Separations

2015

The necessity of reprocessing spent nuclear fuel has arisen from increasing

awareness and concern for the environment in addition to the potential of minimising

proliferation A number of different reprocessing techniques are currently being

developed around the world to allow useful spent nuclear fuel (SNF) to be recycled and

reused and the remaining waste to be treated One such technique currently being

developed in the USA is the TALSPEAK process an advanced reprocessing method for

the separation of trivalent lanthanide (Ln3+

) and minor actinide (MA3+

) components

This process developed in the 1960s at Oak Ridge National Laboratory uses DTPA to

act as a holdback reagent for MA3+

in a lactate buffered aqueous phase at pH 36

allowing Ln3+

to be selectively extracted by organophosphate HDEHP into an organic

phase of DIPB or dodecane

TALSPEAK is one of the most promising techniques being researched due to its

numerous advantages particularly its relative resistance to radiolysis and its ability to

be carried out without the need for high reagent concentrations Additionally it gives

high separation factors in the region of ~50-100 comparable to other advanced

reprocessing methods under development The chemistry of the process is very complex

and not particularly well understood so it would be advantageous to simplify the process

by removing the need for a separate holdback reagent and buffer

In collaboration with colleagues at the Idaho National Lab the use of amino

acids as a potential combined buffer and soft donor was investigated Although it was

found that amino acids do not act as holdback reagents in their own right optimisation

of an L-alanine buffered TALSPEAK system with DTPA was found to allow the

process to be carried out effectively at a lower pH of 2 which is more preferable for

industrial application

As an extension of this separation studies were carried out using the tripeptide

L-glutathione (GSH) to determine its potential for use as a combined buffer and soft-

donor As with the studies with amino acids it was found that GSH also does not act as

a holdback reagent in its own right however it does interact with Ln-DTPA complexes

at pH 4 When optimised at this pH separation factors of up to 1200 were achieved for

Eu3+

Am3+

whilst still maintaining low MA3+

partitioning However further studies by

ICP-MS and luminescence spectroscopy showed that a GSH buffered system was not

effective for extraction of heavier lanthanides although the results show the potential

for further investigation into other short and longer chain peptide buffered systems and

possibly lanthanide-lanthanide separations

Further studies were carried on amino acid appended DTPA ligands which were

synthesised in a one step reaction in order to create a combined buffer and soft donor

The ligands were found to self-buffer at around pH 2 and allow successful separation of

Eu3+

Am3+

(SF ~ 100) The results from initial investigations by luminescence

spectroscopy and solvent extraction are promising and are presented here Further work

is needed on these systems in order to optimise their extraction capability and minimise

Am3+

partitioning In the future this work could promote studies for better

understanding of TALSPEAK chemistry that could be used in industrial partitioning

processes

25

DECLARATION

No portion of the work referred to in the thesis has been submitted in support of an

application for another degree or qualification of this or any other university or other

institute of learning

26

COPYRIGHT STATEMENT

The author of this thesis (including any appendices andor schedules to this thesis) owns

certain copyright or related rights in it (the ldquoCopyrightrdquo) and she has given The

University of Manchester certain rights to use such Copyright including for

administrative purposes

ii Copies of this thesis either in full or in extracts and whether in hard or electronic

copy may be made only in accordance with the Copyright Designs and Patents Act

1988 (as amended) and regulations issued under it or where appropriate in accordance

with licensing agreements which the University has from time to time This page must

form part of any such copies made

iii The ownership of certain Copyright patents designs trade marks and other

intellectual property (the ldquoIntellectual Propertyrdquo) and any reproductions of copyright

works in the thesis for example graphs and tables (ldquoReproductionsrdquo) which may be

described in this thesis may not be owned by the author and may be owned by third

parties Such Intellectual Property and Reproductions cannot and must not be made

available for use without the prior written permission of the owner(s) of the relevant

Intellectual Property andor Reproductions

iv Further information on the conditions under which disclosure publication and

commercialisation of this thesis the Copyright and any Intellectual Property andor

Reproductions described in it may take place is available in the University IP Policy

(see httpdocumentsmanchesteracukDocuInfoaspxDocID=487) in any relevant

Thesis restriction declarations deposited in the University Library The University

Libraryrsquos regulations (see httpwwwmanchesteracuklibraryaboutusregulations) and

in The Universityrsquos policy on Presentation of Theses

27

ACKNOWLEDGEMENTS

Firstly I would like to thank my University supervisors Dr Louise Natrajan and

Dr Clint Sharrad for their support and encouragement during my PhD and for their help

and guidance when needed I would also like to thank Dr Leigh Martin my industrial

supervisor at the Idaho National Lab for the opportunity to work there and gain valuable

new experience

For all of his help in the lab general advice and knowledge on the TALSPEAK

process I would particularly like to thank Dr Travis Grimes from the INL - I could not

have done it without you - and for much of the help and advice I received in

Manchester (as well as lending an ear when I needed to vent) I would like to thank Dr

Adam Swinburne

Thank you also to Dr Andreas Geist for conducting some separation studies for

me at KIT-INE Your contributions have been very valuable and I am most grateful for

all of your help

Sarah Hendley Kevin Beal Andrew Alker and Adrien Moll as Masters and

placement students have helped with various parts of the work in this thesis and

deserve great thanks for their contributions Additionally thank you to Dr Michael

Andrews for helping Adrien so much in the lab whilst I was finishing off my

experiments and beginning to write up my thesis I appreciate the time you spent even

though you had so much to do yourself

Further thanks to Prof Simon Pimblott Greg Horne and Logan Barr for

accommodating me and my Masters students at DCF for irradiation studies and to Greg

especially for giving up your precious time to help us

Dr Tamara Griffiths and Dr Catherine Riddle made working in the lab at the

INL a very enjoyable experience for me and kept me sane and encouraged in times of

desperation Many thanks to you wonderful ladies Also thank you to the Aqueous

Separations and Radiochemistry group (Jack Leigh Peter Travis Rocky Dean Cathy

Bruce Guy and Brandi) Terry Todd and other staff at the INL (Steve Chris Jake all

of the radcons the Analytical group and other placement students) who likewise made

me feel very welcome in a place so far from home

I would additionally like to thank Teams NatrajanMillsSharrad (Sean Adam

Simon Lucy Lizzie Debbie Chloe Mike Pete Kathryn Toria Jen (honorary

member) Dr David Mills Ally Conrad Aruna Helen Tamara Kate Dan Chris

Dave Charles Peter Zana Rich Hugues and Tim) and the Centre for Radiochemistry

28

Research at the University of Manchester for general lab help and support and for

making Manchester a great place to work And to my conference buddies Tamara

Debbie Kate and Adam for making conferences as much about the social side as the

work

Thank you to the INL KIT and Diamond Light Source for the opportunities to

carry out work using their specialist equipment and to Dr Louise Natrajan Dr Sean

Woodall Dr Daniel Whittaker Dr Tamara Griffiths Dr Clint Sharrad Dr Leigh Martin

and Dr Travis Grimes for helping with some of the work carried out

I could not have done this PhD without funding from Batelle Energy Alliance

through the INL and the University of Manchester so thank you

On a personal note a big thank you to Steph my room mate for making my 9

months living in Idaho so much fun And also to Cathy and Glen Shelby Natalie and

Leigh and Marie for all the fun times too Lastly but not least I would like to give huge

thanks to my (non-chemistry non-Idaho) friends and family for their support over the

past 4 years especially my wonderful husband Lee - youre amazing and my rock as

always - and my parents for everything over the past 26 years

It was worth it in the end

29

LIST OF SYMBOLS amp UNITS

gt greater than

˂ less than

plusmn plus or minus

percent

degC degrees Celsius

α alpha

β beta

γ gamma

δ chemical shift

Δ change in

ε molar extinction coefficient

λ wavelength

microL microlitres

micros microseconds

ρ density

τ lifetime

ν frequency

ν= energy level

wavenumber

Aring angstroms

A proportionality constant for q taking into account the

inner hydration sphere

ABS optical density difference between ODi and ODb

amu atomic mass units

au arbitrary units

B correction factor for q taking into account the outer

hydration sphere

Bq Becquerel

cm centimetres

D (pD D2O MeOD) deuterium

dm3 decimetres cubed (litres)

E energy

F Faradays constant

30

g grams

G critical dose value

Gy Gray

h Plancks constant

Hz Hertz

J Joules

J= rotational energy level

K Kelvin

kBq kiloBecquerel

kg kilograms

kGy kiloGray

kJ kiloJoules

L litres

log β stability constant

M molar (moldm-3

)

mg milligrams

MHz megaHertz

min minute(s)

mL millilitres

mm millimetres

mM millimolar

mol moles

mmol millimoles

ms milliseconds

ng nanograms

nm nanometres

ns nanoseconds

ODi optical density of irradiated solution

ODb optical density of non-irradiated control solution

ppm parts per million

s seconds

t time

Zeff effective nuclear charge

31

LIST OF ABBREVIATIONS amp ACRONYMS

An actinides

aq aqueous

BT nack-energy Transfer

BTBP bis-triazinbipyridine

BTP bis-triazinylpyridine

CEA Commissariat agrave lrsquoEacutenergie Atomique et aux Eacutenergies

Alternatives

CE-ICP-MS capillary electrophoresis ndash inductively coupled plasma ndash

mass spectrometry

cf confer Latin compare

CMPO carbomoylmethylphosphine oxide

CP corrosion products

CYANEX 301 bis(244-trimethylpentyl)phosphinodithioic acid

CyMe4-BTBP 66-bis(5588-tetramethyl-5678-tetrahydrobenzo

[e][124]triazin-3-yl)-22-bipyridine

D distribution ratio

DCF Dalton Cumbrian Facility

DEPT distortionless enhancement by polarization transfer

DFT density functional theory

DIAMEX DIAMide EXtraxtion

DIPB diisopropyl benzene

DMDBTDMA dimethyldibutyltetradecylmalonamide

DMDOHEMA dimethyldicotylhexylethoxymalonamide

DMF dimethylformamide

DNA deoxyribonucleic acid

DO3A 147 tris(carboxymethyl) 14710 tetraazacyclododecane

DOTA 14710-tetraazacyclododecane-14710-tetraacetic acid

DTPA diethylenetriaminepentaacetic Acid

EC electron capture

EDTA ethylenediaminetetraacetic acid

eg exempli gratia Latin for example

ET electron transfer

32

et al et alli Latin and others

EURACT-NMR Transnational Access to Unique European Actinide and

Radiological NMR Facilities

EXAm EXtraction of Americium

FP fission products

GANEX Grouped ActiNide EXtraction

GSH glutathione

HDEHP (di-(2ethylhexyl)phosphoric acid

HEH[ΦP] (2-ethylhexyl)phenylphosphonic acid

HEH[EHP] (2-ethylhexyl)phosphonic acid mono-2-ethylhexyl ester

HEDTA (2-hydroxyethyl) ethylenediaminetatraacetic acid

HSQC heteronuclear single quantum correlation

I ionic strength

IC internal conversion

ICP-MS inductively coupled plasma ndash mass spectrometry

ie id est Latin that is

INL Idaho National Laboratory

IR infra-red

iSANEX Innovative SANEX

ISC inter-system crossing

KIT-INE Karlsruhe Institute of Technology - Institut fuumlr Nukleare

Entsorgung (Institute for Nuclear Waste Disposal)

Lac lactate

LASER light amplification by stimulated emission of radiation

LINAC linear accelerator

Ln lanthanides

LUCA Lanthaniden Und Curium Americium trennung

LWR light water reactor

M metal

MA minor actinides

MALDI-MS matrix-assisted laser desorption ionization mass

spectrometry

MOX mixed oxide

MRI magnetic resonance imaging

Nd-YAG neodymium-yttrium aluminium garnet

33

nIR near-infra-red

NMR nuclear magnetic resonance

NPH normal paraffinic hydrocarbon

NR non-radiative decay

org organic

PPE personal protective equipment

PUREX Plutonium and Uranium Refinement by EXtraction

q number of solvent molecules in the inner hydration sphere

SANEX Selective ActiNide EXtraction

SF separation factor

SNF spent nuclear fuel

SX solvent extraction

TALSPEAK Trivalent Actinide Lanthanide Separation by Phosphorus

reagent Extraction from Aqueous Complexation

TALSQuEAK Trivalent Actinide Lanthanide Separation using Quicker

Extractants and Aqueous Complexes

TBP tributyl phosphate

TEA triethylamine

TEDGA NNNrsquoNrsquo-tetraethyl-diglycolamide

TEHP tris(2-ethylhexyl)phosphate

TM transition metals

TODGA tetraoctyldiglycolamide

TPH tetrapropylene hydrogenated

TRLFS time-resolved LASER-induced fluorescence spectrocopy

TRPO trialkylphosphine oxide

TRUEX TRans-Uranic EXtraction

TTHA triethylenetetramine hexaacetate

SF spontaneous fission


UoM The University of Manchester

UV ultra-violet

UV-vis ultra-violet-visible

vs versus Latin against

XAS x-ray absorption spectroscopy

34

AMINO ACID ABBREVIATIONS

Amino Acid 3 Letter Abbreviation

Alanine Ala

Arginine Arg

Asparagine Asn

Aspartic acid Asp

Cysteine Cys

Glutamic Acid Glu

Glutamine Gln

Glycine Gly

Histidine His

Isoleucine Ile

Leucine Leu

Lysine Lys

Methionine Met

Phenylalanine Phe

Proline Pro

Serine Ser

Threonine Thr

Tryptophan Trp

Tyrosine Tyr

Valine Val

35

1 INTRODUCTION


111 Background

The ldquorare earthrdquo or lanthanide elements (Ln) can be found between barium and

hafnium in the periodic table in the first of the two rows containing the f-block

elements The f-block elements are all metallic and have 4f or 5f valence electron

subshells the lanthanides Ce-Lu are also often referred to as the ldquo4frdquo elements1

Although often considered to be part of the lanthanide series lanthanum is not usually

considered to be a ldquo4frdquo element as it has no f-electrons The 4f elements all have

relatively high abundances despite often being termed the ldquorare earthrdquo elements except

for promethium (Pm) which is radioactive and does not occur in nature2 All of the 4f

elements except promethium were discovered and had all successfully been isolated by

the early 20th

century Promethium was not discovered until 19473

The actinide elements (An) can be found between radium and rutherfordium in

the periodic table and are also known as the 5f elements as their valence shell is the 5f

shell They are all radioactive as none of them have any stable isotopes Although often

considered to be part of the actinide series actinium is not usually considered to be a

ldquo5frdquo element due to its electronic configuration of 5f 0 Despite this thorium which also

has a ground state electronic configuration of 5f 0 is considered to be a 5f element The

first actinide element to be discovered was uranium which was discovered in 1789 by

Klaproth in the mineral pitchblende Thorium and protactinium had also both been

discovered by 1913 but the later actinides were not synthesised until the Second World

War initially by Seaborg4

112 Sources of the Lanthanides and Actinides

The naturally occurring lanthanide elements are found in two minerals

primarily monazite and bastnaumlsite which are ores of mixed lanthanide metals and have

the general formulae LnPO4 and LnCO3F respectively Monazite also contains

radioactive thorium so is the less favourable of the two sources of lanthanides

commercially5

Ac Th Pa and U are the only naturally occurring actinide (An) elements

Uranium is less abundant than thorium (24 ppm vs 81 ppm) in the Earthrsquos crust but is

found in numerous minerals in oxide form including pitchblende (uraninite) and

36

carnotite Protactinium is one of the rarest elements in the world and is found at trace

levels in some uranium ores

The remaining 11 (Np-Lr) elements in the An series must be synthesised

Neptunium to fermium can be synthesised by neutron bombardment whereby a neutron

is captured by a heavy element atom and a γ-ray is emitted This is followed by the

emission of a β- particle in a β

- decay process to form a new element with an increased

atomic mass (see Scheme 11) However as this is a relatively improbable process

synthesis of the heaviest elements is impossible by this method and so synthesis of the

heavier elements is carried out by bombardment with light atoms although again this is

also an unfavourable reaction6

238U (n γ)

239U rarr

239Np rarr

239Pu (n γ)

240Pu (n γ)

241Pu rarr

241Am (n γ)

242mAm rarr

242Cm

Scheme 11 Formation of 242

Cm by a series of neutron capture and β- decay

processes6


The shapes of the f -orbitals have a variety of different representations dependent

on molecular symmetry The electron configurations for the metals and Ln3+

ions can be

seen in Table 11 along with values for the third and fourth ionisation energies

Gadolinium (Gd) and lutetuim (Lu) both have a 5d electron giving more stable half-full

or full 4f orbitals respectively Cerium (Ce) is also thought to possess a 5d electron The

most common oxidation state for the lanthanide ions is +3 whereby both of the 6s

electrons and either the 5d electron (if applicable) or one 4f electron are lost The first

two ionisation energies of the lanthanide elements are all relatively low corresponding

to the removal of the 6s electrons The third ionisation energy is also sufficiently low to

allow the generation of the Ln3+

ion in each case by removal of the 5d electron or a 4f

electron The fourth ionisation energies are generally significantly higher as the 4f

orbital becomes more stabilised as the first three electrons are removed This makes the

+4 oxidation state rare but can be formed by Ce Pr and Tb under certain conditions

Samarium (Sm) europium (Eu) and ytterbium (Yb) can form Ln2+

ions relatively

readily

β- β

- β

- β

-

23 mins 23 days 13 years 16 hours

37

Table 11 Electronic properties of the lanthanides 7

Symbol Name Electron

Configuration

(Metal)

Electron

Configuration

(Ln3+

)

3rd

Ionisation

Energy

(kJmol-1

)

4th

Ionisation

Energy

(kJmol-1

)

La Lanthanum [Xe]5d16s

2 [Xe] 1850 4819

Ce Cerium [Xe]4f15d

16s

2 [Xe]4f

1 1949 3547

Pr Praseodymium [Xe]4f36s

2 [Xe]4f

2 2086 3761

Nd Neodymium [Xe]4f46s

2 [Xe]4f

3 2130 3899

Pm Promethium [Xe]4f56s

2 [Xe]4f

4 2150 3970

Sm Samarium [Xe]4f66s

2 [Xe]4f

5 2260 3990

Eu Europium [Xe]4f76s

2 [Xe]4f

6 2404 4110

Gd Gadolinium [Xe]4f75d

16s

2 [Xe]4f

7 1990 4250

Tb Terbium [Xe]4f96s

2 [Xe]4f

8 2114 3839

Dy Dysprosium [Xe]4f10

6s2 [Xe]4f

9 2200 4001

Ho Holmium [Xe]4f11

6s2 [Xe]4f

10 2204 4100

Er Erbium [Xe]4f12

6s2 [Xe]4f

11 2194 4115

Tm Thulium [Xe]4f13

6s2 [Xe]4f

12 2285 4119

Yb Ytterbium [Xe]4f14

6s2 [Xe]4f

13 2415 4220

Lu Lutetium [Xe]4f14

5d16s

2 [Xe]4f

14 2022 4360


As previously stated the valence electron sub-shell for the actinides is the 5f

shell The electron configuration of the actinides is shown in Table 12 Thorium has no

5f electron but has 6d2 configuration as an empty 5f shell is more favoured Curium has

a 6d electron giving rise to a more stable half full 5f subshell

The actinide elements have a wide range of available oxidation states

particularly for the earlier metals For the heavier elements however the most common

oxidation state for the metal ions is +3 having lost both of the 7s electrons and either a

6d electron (if applicable) or one 5f electron The available oxidation states for each of

the actinides can be seen in Table 13 Ionisation energy values are not available for all

of the actinides although the standard electrode potentials for the reduction of An4+

to

An3+

and An3+

to An2+

can be used to give an indication of the ion stabilities The +4

38

oxidation state is the most favoured for Th as it gives rise to empty 6d and 7s shells but

An4+

generally becomes less favoured across the series and may only be found in

solution for americium and curium complexes Conversely the stability of the +2

oxidation state generally increases across the series with an irregularity at Cm which

does not have an available +2 oxidation state due to the stability of the half full 5f

subshell of Cm3+

The variety of oxidation states found in the earlier actinides suggests

that all of the valence electrons are available for bonding in these elements7

Table 12 Electronic properties of the actinides7


Config

(Metal)

Electron

Config

(An2+

)

Electron

Config

(An3+

)

Electron

Config

(An4+

)

Th Thorium [Rn]6d27s

2 NA [Rn]6d

1 [Rn]

Pa Protactinium [Rn]5f26d

17s

2 NA [Rn]5f

2 [Rn]5f

1

U Uranium [Rn]5f36d

17s

2 NA [Rn]5f

3 [Rn]5f

2

Np Neptunium [Rn]5f46d

17s

2 NA

[Rn]5f

4 [Rn]5f

3

Pu Plutonium [Rn]5f67s

2 NA [Rn]5f

5 [Rn]5f

4

Am Americium [Rn]5f77s

2 [Rn]5f

7 [Rn]5f

6 [Rn]5f

5

Cm Curium [Rn]5f76d

17s

2 NA [Rn]5f

7 [Rn]5f

6

Bk Berkelium [Rn]5f97s

2 NA [Rn]5f

8 [Rn]5f

7

Cf Californium [Rn]5f10

7s2 [Rn]5f

10 [Rn]5f

9 [Rn]5f

8

Es Einsteinium [Rn]5f11

7s2 [Rn]5f

11 [Rn]5f

10 [Rn]5f

9

Fm Fermium [Rn]5f12

7s2 [Rn]5f

12 [Rn]5f

11 [Rn]5f

10

Md Mendelevium [Rn]5f13

7s2 [Rn]5f

13 [Rn]5f

12 [Rn]5f

11

No Nobelium [Rn]5f14

7s2 [Rn]5f

14 [Rn]5f

13 NA

Lr Lawrencium [Rn]5f14

6d17s

2 NA [Rn]5f

14 NA

39

Table 13 Available oxidation states of the actinides and colours of ions in solution

where applicable Ions in black text are either not found in aqueous solution or are

unknown8


Relativistic effects are much more important for heavy elements than light

elements as they are proportional to an atomrsquos mass The Special Theory of Relativity

as devised by Einstein shows that as the velocity (ν) of a particle increases towards the

speed of light (c) its mass (m) increases to infinity as shown in equation 11 where m0

is the rest mass of the particle This is the relativistic mass increase

Equation 11

For example the relativistic mass increase of a 1s electron in uranium (found to

be 135 me) can be calculated using the average radial velocity of the electrons (νrad)

which is roughly equivalent to the atomic number Z for 1s electrons and the rest mass

of an electron (me) This is shown in equation 12

Equation 12

This effect causes a contraction of 1s electron subshell due to the inverse

relationship between electron mass and the Bohr radius of an atom meaning that the

shell is held more closely to the nucleus and stabilised A similar effect is true for p

electrons The relationship can be seen in equation 13 where α0 is the Bohr radius e is

the elementary charge and ħ is the reduced Planckrsquos constant

Equation 13

7 NpO23+

PuO23+

AmO65-

6 UO22+

NpO22+

PuO22+

AmO22

+5 PaO2

+UO2

+NpO2

+PuO2

+AmO2

+

4 Th4+

Pa4+

U4+

Np4+

Pu4+

Am4+

Cm4+

Bk4+

Cf4+

3 Ac3+

Th3+

Pa3+

U3+

Np3+

Pu3+

Am3+

Cm3+

Bk3+

Cf3+

Es3+

Fm3+

Md3+

No3+

Lr3+

2 Am2+

Cf2+

Es2+

Fm2+

Md2+

No2+

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Most stable in aqueous solution Accessible Only found in solid complexes

40

This explains why relativistic effects are more significant for larger nuclei as the

mass increase is dependent on Z Conversely to the stabilisation of s and p electrons by

relativistic effects valence f and d orbitals are expanded further from the nucleus and

destabilised due to effective shielding of the s and p electrons of the nucleus The effect

is greater in the actinides due to the increased number of electrons and is responsible for

the variety of oxidation states exhibited by An as the valence 5f electrons are further

from the nucleus and are therefore more available for bonding Relativistic effects are

much less important for the lanthanides than the actinides as the actinides are more

destabilised by the effects7


There is a general decrease in the size of the metallic and ionic radii of the

lanthanides across the series explained by the fact that 4f electrons are considered to be

ldquocore-likerdquo so are not available for bonding This causes crystal field effects to be minor

in lanthanide complexes The ldquocore-likerdquo property of the 4f electrons prevents them

from shielding valence electrons in outer subshells from the nucleus allowing the

effective nuclear charge (Zeff) to increase and causing contraction of the atoms and ions

across the series The lanthanide contraction is responsible for the small size difference

between the second and third row transition metals

The ionic radii of the actinides for the +3 +4 and +5 oxidation states gradually

decrease in size across the series although the metallic radii do not follow the same

trend The effect of the trend on the chemistry of the elements is not well known as the

later elements cannot be made with large enough yields to study and they decay too

rapidly The gradual decrease is due to the fact that 5f-electrons are poor at shielding s

and p electrons from the nucleus due to their greater radial extension allowing the

effective nuclear charge (Zeff) to increase and the s and p electrons to be held more

closely to the nucleus

117 Co-ordination Chemistry of the Lanthanides and Actinides in Solution

Lanthanide ions are hard Lewis acids and so co-ordinate readily with hard bases

The core-like nature of the 4f electrons prevents them from interacting significantly with

ligand orbitals and means that lanthanide complexes are bonded electrostatically The

co-ordination geometry of complexes is therefore determined predominantly by the

steric interactions of the ligands The high charge density of the Ln3+

ions allows them

41

to form ionic bonds however this means that many lanthanide complexes are labile in

solution

Actinide ions are also hard Lewis acids co-ordinating easily with hard bases

The greater radial extension of the 5f electrons caused by relativistic effects gives rise

to greater chemical activity in the actinides than the lanthanides as the 5f electrons are

more available for bonding This also explains the tendency of the early actinides to

form covalent bonds however the later actinides mainly interact electrostatically like

the lanthanides

Actinide ions are found as An3+

for the later elements in the series except for

No which is found as No2+

and they behave much like the lanthanides However for

some of the early actinides linear actinyl ions (AnO2+ and AnO2

2+) can be observed in

addition to free ions and are often more stable particularly for U91011

Lanthanide and actinide complexes often have high co-ordination numbers

typically 8 or 9 in aqueous solution (although co-ordination numbers as high as 12 have

been reported) due to their large size The Ln3+

ion forms readily in aqueous solution

and the An3+

ion is the common form for the later actinides however the solution state

chemistry of the early actinide ions is complicated Americium is mainly found in the

+3 oxidation state in solution although it also forms the AmO22+

ion The Am7+

oxidation state has been known to exist but is unstable except in very alkaline

conditions

It is difficult to determine the exact co-ordination numbers and geometries of Ln

and An ion complexes in solution due to the lability of the complexes particularly for

lanthanides

1171 Hydrolysis

The solvation of metal cations by water particularly cations with a high charge

density such as Ln3+

and An3+

ions will result in some hydrolysis The cations polarise

the O-H bonds of the solvent allowing the hydrated metal cations to act as Broslashnsted

acids An example can be seen in Equation 14

Equation 14 [Eu(H2O)8]3+

+ H2O rarr [Eu(H2O)7(OH)]2+

+ H3O+

The acidity of the Ln3+

cations increases across the series as the charge density

increases For the An ions the acidity increases as follows

AnO2+ lt An

3+ lt AnO2

2+ lt An

4+

42

Generally the acidity increases with increasing charge density like Ln The

position of AnO22+

can be explained by the fact that the O2-

ions do not fully reduce the

charge on the An ion and so the effective charge of the ion is seen to be +331


Substituting water for other monodentate ligands in aqueous solution is

challenging for lanthanides as the complexes are labile and the high charge density of

the ion and affinity for a polar environment means that it will often remain solvated

Isolating monodentate complexes from water is almost impossible as Ln3+

ions having a

high enthalpy of hydration making complex formation endothermic Complexation can

be achieved much more easily by the use of macrocyclic or chelating ligands

Conversely it is much easier to form monodentate actinide complexes in water

such as salts which will become hydrated rather than completely substituted by water

molecules However complexation is still much easier with macrocycles or chelates in

aqueous solution12


When a chelate or macrocycle ligates to an ion the reaction entropy increases as

water molecules are eliminated from the complex (see Equation 15) which is

thermodynamically favourable As a chelating or macrocyclic ligand bonds to the metal

ion the remainder of the ligand is considered to be in close proximity to the ion giving

it an ldquoartificially highrdquo concentration and is therefore more likely to bond than

surrounding ions or ligands


+ EDTA4-

rarr [Eu(EDTA)(H2O)3]- + 6H2O

Chelating complexes increase in stability across lanthanide and actinide series

This is because the Coulombic attraction between the ligand and the metal increases

with charge density However there is a slight irregularity in this trend for the

lanthanides where a slight dip can be seen at Gd3+

as this is thought to be the point at

which the co-ordination number changes from 9 to 8 often referred to as the

lsquogadolinium breakrsquo12

43



Most lanthanide and actinide complexes are paramagnetic as they have unpaired

electrons The nuclei of paramagnetic complexes are subjected to a local magnetic field

in addition to the field generated by the spectrometer causing the complexes to have

larger chemical shifts NMR spectra of paramagnetic complexes often have broad peaks

as they have faster spin-lattice relaxation times due to strong spin-orbit coupling13

The

relationship is explained by the Heisenberg Uncertainty Principle which links energy

(E) and time (t) in Equation 16 where h is Planckrsquos constant

Equation 16

Considering the relationship between energy and frequency (ν) in Equation 17

the Heisenberg equation can be rearranged to show the inverse relationship between the

change in frequency (Δν) or ldquospectral linewidthrdquo (defined as the peak width of the

signal at half of its maximum height) and the lifetime of the excited state or in this case

spin-lattice relaxation time (Δt) See Equation 1814

Equation 17

Equation 18



Fluorescence and phosphorescence are both types of luminescence Radiation is

used to excite electrons into a higher electronic energy level which then emit photons

(light) as they relax back down to their ground state Fluorescence is a relatively fast

process (picoseconds to milliseconds) as it is an allowed transition by the spin selection

rule not involving a change in spin multiplicity Phosphorescence is a slower process

(milliseconds to seconds) as it does involve a change in electron spin from a singlet to a

triplet excited state ndash it is formally ldquospin-forbiddenrdquo The processes can be seen in the

Jablonski diagram in Figure 11 By contrast f-f transitions whereby f-electrons are

excited into other f-subshells are formally Laporte forbidden so direct excitation of the

4f electrons is unfavourable These rules are relaxed a little by vibronic (vibrational and

44

electronic) coupling in which a vibration in the molecule causes the temporary

lowering of the symmetry of the metal allowing the d and p orbitals to share symmetry

The transition has some drarrp character and so becomes more intense However for

vibronic coupling to take place the valence orbitals must interact with incoming

ligands For the transitions that occur in the visible region of the spectrum this explains

why the colours of Ln3+

ions are weak as the valence 4f shell interacts poorly with

ligands due to their core-like nature Vibronic coupling is greater in actinide ions

Figure 11 Jablonski diagram showing fluorescence and phosphorescence15


Lanthanide ions in which f-f transitions can occur are luminescent and emit

across a range of the electromagnetic spectrum from the Ultra-Violet (UV) range to the

visible (vis) or near-infra-red (nIR) region of the spectrum (Table 14) La3+

does not

possess any f-electrons and Lu3+

has a full 4f shell so these two ions are not

luminescent

45


Luminescent ions which emit

in the nIR region of the

spectrum

Colours of luminescent ions

which emit in the visible and

UV regions of the spectrum

Pr3+

Sm3+

Nd3+

Eu3+

Ho3+

Tb3+

Er3+

Dy3+

Yb3+

Tm3+

Gd3+

(UV)

Ce3+

(UV)

Lanthanide ions have long luminescence lifetimes as their transitions are

formally forbidden Since the interaction between the metal ion and the ligand is

negligible in lanthanides the emission spectra of lanthanide complexes have narrow

emission lines resembling the spectra of the free ions Solid lanthanide compounds and

complexes also tend to be luminescent1617


Actinide ions in which f-f transitions can occur are luminescent and also emit

across a range of the electromagnetic spectrum from the UV range to the infra-red IR or

nIR region (Table 15) Ac3+

and Th4+

do not have any f-electrons and Lr3+

has a full 4f

shell so these two ions are not luminescent No luminescence studies have been

performed on Fm3+

Md3+

or No2+

The remaining An have luminescent ions but studies

have been most widely performed on UO22+

Am3+

and Cm3+

as these are the most

widely available have fewer problems associated with radioactivity and safety and are

the most well understood

46



in the IRnIR region of the

spectrum

Colours of luminescent ions which

emit in the visible and UV regions

of the spectrum

NpO22+

Pa4+

(UV) Pa4+

Pa4+

Pa4+

Pa4+

Am3+

U4+

(UV) U4+

Es3+

UO2+

UO22+

UO22+

UO22+

UO22+

Am3+

Am3+

Am3+

Am3+

Cm3+

Bk3+

Cf3+

Unlike lanthanides actinide emission spectra and lifetimes vary depending on

the species and bound species or counter ions although most lifetimes for An are short

(lt 20 ns) with the exceptions of the 5f0 species UO2

2+ (which has lifetimes varying

from 130 ns to 300 μs) and Cm3+

which has a lifetime of ~65 μs and is known to have

the highest luminescence quantum yield of the An ions allowing it to be studied in very

low concentrations which is useful due to its low availability Luminescence studies on

solid state An compounds are unreliable as they are susceptible to radioluminescence

whereby the energy released by radioactive decay can result in the generation of an

emissive excited state718

1224 Sensitised Luminescence and Antennae

Sensitisation of luminescence can occur if an ldquoantennardquo is present which is a

sensitising chromophore An electron is excited on the ion by energy transferred from

the chromophore The antenna must be in close proximity to the ion for energy transfer

to take place and so antennae are usually used as ligands

Antennae are predominantly organic aromatic materials bonded to macrocycles

(as these are easier to ligate to the metal ions in solution) During sensitisation an

electron from the chromophore is excited from its ground state to a singlet excited state

Energy may then be transferred to a triplet excited state by inter-system crossing (ISC)

where the potential curves of the two states intersect at similar energies Although this

spin forbidden spin orbit coupling makes it possible by slightly shifting the electronrsquos

energy levels Energy from the triplet state is then transferred to the metal ionrsquos excited

47

state The ion can then relax to its ground state by luminescence This is the most

common pathway for sensitised emission however it is possible to transfer energy

directly from the singlet excited state on the chromophore to the ion (Figure 12)

Figure 12 Energy transfer pathway for sensitised luminescence of Ln3+

complexes 1S

represents an excited singlet state 3T an excited triplet state and f and frsquo represent

excited states of the Ln3+

ion 19


ldquoTerm symbolsrdquo are used to label ground state and excited state energy levels

for lanthanide ions Term symbols are derived from Russell-Saunders coupling and

account for the net atomic orbital angular momentum and the net spin angular momenta

of the state determined from the sum of the individual angular momenta of an ionrsquos

electrons Term symbols take the form

(2S+1)LJ

where S is the spin multiplicity of the state L corresponds to the ldquolrdquo quantum number

for the state and J is the coupling of L and S Excited states have several possible J

values although the ground state always has a single J value which can be determined

by Hundrsquos rules The Russell-Saunders coupling scheme is only useful for lanthanide

ions and cannot be applied to actinide ions as spin-orbit coupling is much greater in An

and the 5f orbitals have different properties to the 4f orbitals in particular the greater

importance of relativistic effects (see Section 115) However Russell-Saunders terms

have been used as a basis for assigning ground and excited state terms20

F = Fluorescence P = Phosphorescence L = Luminescence NR = Non Radiative Decay ISC = Inter System Crossing ET = Energy Transfer BT = Back-energy Transfer IC = Internal Conversion

48

1226 Quenching

The excited states of the trivalent lanthanides and actinides are readily quenched

in solution Quenching occurs when the vibrational energy levels of high energy

oscillators (such as C-H N-H or O-H bonds) within the molecule or its environment

(solvent) have a similar energy to the excited state of an ion Inter-System Crossing

(ISC) from the excited state to these vibrational levels can occur causing non-radiative

decay preventing luminescence The efficiency of this non-radiative decay is dependent

upon the energy gap between the emissive state and the ground state of the ion and also

on the number of quanta (energy levels) of the oscillator If the non-radiative decay is

favourable and happens faster than luminescence quenching will occur Quenching

reduces the intensity lifetime and quantum yield of luminescence If the ionrsquos emissive

state is close in energy to the triplet excited state of the ligand (lt 20000 cm-1

) thermal

quenching may also occur whereby energy is transferred backwards to the triplet

excited state of the chromophore21


Tb3+

is less susceptible to vibrational quenching than other lanthanide ions as the

energy gap between the lowest emissive state and the ground state of Tb3+

is very high

(20500 cm-1

) It is however susceptible to thermal quenching and back energy transfer

Eu3+

also has a large energy gap (17250 cm-1

) This results in a relatively greater

emission intensity for these ions

Other lanthanide ions such as Pr3+

Ho3+

Er3+

Tm3+

Yb3+

Dy3+

and Sm3+

with

smaller energy gaps are more easily quenched giving less intense emission Er3+

has the

smallest energy gap close to the υ=0 energy level of O-H so is the most easily

quenched (see Figure 13) The lower energy levels of the oscillators provide better

overlap with the energy levels of the ions due to a better overlap with the wavefunction

therefore ions which have energy levels that overlap with the lower quanta of the

oscillators will also be more easily quenched Gd3+

has the highest energy gap of the

lanthanide ions (32000 cm-1

) and cannot be sensitised by conventional UV absorbing

chromophores

49

Nd3+Eu3+ Tb3+Yb3+ O-H O-DTm3+ Sm3+ Pr3+ Er3+

3H4

4I132

4I112

3H4

3H5

3H6

3H6

3H5

3H4

0

20000

4I92

4I112

4I132

4I152

4F32

2H92

4S32

4F92

2H112

4G52

4G72

4G92

(2D2P)32

4G1125D4

7F07F17F27F37F4

7F5

7F67F0

7F1

7F2

7F3

7F4

7F5

7F6

5D0

5D1

5D2

2F52

2F72

10000

6H52

6H72

6H92

6H112

6H132

4F32

4G52

4F32

4F12

4F52

4F72

4G72

4F92

4F112

3F2

3F4

3P0

3P1

3F3

1I6

1G4

4I92

4F92

4S32

4F72

3F4

3F3

3F2

1G4

E

cm

-1

=0

=1

=2

=3

=4

=5

=0

=1

=2

=3

=4

=5

=6

=7

2H112

1D2

Figure 13 Energy level diagram showing the ground and excited states of a selection

of lanthanides and vibrational oscillators Emissive states are shown in red The energy

levels of O-H and O-D oscillations are shown in blue22

Actinides are also susceptible to quenching even more so than the lanthanides

as all of them have smaller energy gaps between the lowest emissive state and the

ground state The energy gaps of some actinides compared to lanthanides can be seen in

Figure 14

50

Figure 14 The energy gaps between the lowest emissive states and ground

states of a selection of lanthanides and actinides represented by arrows23


In addition to quenching by vibrational oscillators on ligands luminescence can

also be quenched by solvents High energy oscillators must therefore be eliminated from

the solvent in order for luminescence to take place in the solution phase This is

generally achieved by using deuterated (or fluorinated) solvents such as D2O It is also

important to use strongly co-ordinating solvents that would replace the labile ligands

The Horrocks equation can be used to calculate the number of co-ordinated solvent

molecules (q) to an ion whether it is a free ion or co-ordinated to a ligand The original

Horrocks equation (Equation 19) and modified Horrocks equation for q lt 2 (Equation

110) are shown below

Equation 19

Equation 110

The Horrocks equation uses the emission lifetimes (τ) to determine q A is the

proportionality constant taking into account the inner hydration sphere and B is a

correction factor taking into account the outer hydration sphere A and B values are

experimentally determined constants and are available for Sm3+

Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+

Inner sphere hydration (q) values can be effectively determined from

51

solutions of water and methanol For the original Horrocks equation A = 105 for Eu3+

and A = 42 for Tb3+

and for the modified Horrocks equation (when q lt 2 ) A = 12 ms

and B = (025 ndash 0075x) ms-1

(where x = the number of exchangeable N-H oscillators)

for Eu3+

and A = 5 ms and B = 006 ms-1

for Tb3+

242526

13 Nuclear Theory

131 Nuclear Power

Currently all nuclear energy irrespective of use is generated by nuclear fission

Nuclear fission is the splitting of a fissile nucleus into two smaller nuclei often aided by

the collision of an incoming particle or neutron The nucleus captures the neutron

which makes it unstable and it breaks into two fragments The splitting process releases

more neutrons which may continue to cause fission of more nuclei generating a chain

reaction An example of a chain reaction caused by 235

U fission can be seen in Figure

15


U into 92

Kr and 141

Ba27

Fission of heavy radioactive actinide elements is exothermic and a chain

reaction can occur if there are enough fissile nuclei present The amount of fissile

material required for a self-sustaining chain reaction is the ldquocritical massrdquo and any mass

above this is referred to as a ldquosupercritical massrdquo which if not controlled can lead to a

runaway chain reaction and a nuclear explosion

52

235U fission is used to generate nuclear power The fission products (FP) collide

with other atoms and their kinetic energy in converted into heat which is absorbed by

the cooling water and then used to drive steam turbines to generate electricity Control

rods are used in the reactor to control the neutron flux and prevent a runaway chain

reaction These are often made of boron nitride which is a neutron absorber

Moderators are also used to slow down the neutrons to the optimum energy for fission

(~2 kJ mol-1

) and these tend to be light nuclei (12

C or 2H)


Uranium is mined in its ore form from the ground mainly in Middle Eastern

countries Canada Australia and Africa The ore is then milled to extract the uranium as

ldquoyellowcakerdquo which is mixed oxides of triuranium octoxide (U3O8) uranium dioxide

(UO2) and uranium trioxide (UO3) by leaching with acid or alkali followed by

precipitation The remaining ore ldquotailingsrdquo are disposed of as radioactive waste

The yellowcake is then further processed as only 07 of uranium is fissile

235U the dominant isotope is

238U The uranium oxide is enriched by increasing the ratio

of 235

U238

U to approximately 35-5 235

U This is done by converting all of the mixed

oxides into uranium dioxide and then to uranium hexafluoride (UF6) gas and separating

it into two streams ndash one of which is enriched in 235

U and the other depleted

The enriched UF6 is then converted back to UO2 which can be pressed and

heated to 1400 degC to form fuel pellets The depleted uranium is treated as waste The

fuel pellets are subsequently encased in metal rods which can then be used in a fuel

assembly in a reactor

After 18-36 months the build-up of fission products is such that the efficiency

of the fuel decreases so the fuel rods are removed and replaced The used fuel is then

stored for months or years in water which absorbs the heat until the radiation levels

decrease sufficiently for it to be disposed of or reprocessed As there are no disposal

facilities at present for nuclear fuel waste it is simply isolated from the environment

and left in storage until facilities become available28

A diagram of the Nuclear Fuel

Cycle can be seen in Figure 16

The once-through or ldquoopenrdquo fuel cycle whereby waste is stored for disposal is

favoured by a number of countries including Canada parts of Europe and the USA

presently although some research on reprocessing techniques is being carried out in

these areas as reprocessing is becoming increasingly important for the future of nuclear

power A ldquoclosedrdquo fuel cycle whereby the waste is recycled and reused is becoming

53

more and more favoured as a result of this and has been performed in some parts of the

world for many years including the UK and other parts of Europe Russia and Japan29

Figure 16 The Nuclear Fuel Cycle30


The reprocessing of spent nuclear fuel (SNF) is essential for preventing the

exhaustion of uranium supplies and reducing the volume and radiotoxicity of the waste

produced

Current reprocessing techniques involve the removal of re-usable uranium and

plutonium present in the waste which can be recycled and reused together in mixed

oxide (MOX) reactors to produce more nuclear power31

The amount of waste

remaining in storage at present worldwide that could be reprocessed is approximately

200000 tonnes with a global reprocessing capacity of around 4000 tonnes per year

90000 tonnes have been reprocessed over the last 50 years

In addition to the reusable U and Pu in the spent nuclear fuel (SNF) there are

also a variety of other fission products (FP) present such as minor actinides (MA) Np

Am and Cm Ln and transition metals (TM) in addition to corrosion products (CP)

54

from steel containers and pipes in the system as a result of radiolysis erosion and

ageing of equipment These are TM chiefly cobalt (Co) chromium (Cr) iron (Fe) and

manganese (Mn) The composition of SNF can be seen in Table 16 Recently research

into the removal of the other actinides from the waste has become important in order to

transmute them into shorter-lived radionuclides so that their radioactivity will not

persist for as long making the disposal process easier and faster This coupled with a

similar approach for any remaining plutonium will make the waste proliferation

resistant as it would not allow the Pu to be recovered from storage in the future for

proliferation purposes

Table 16 Approximate compositions of SNF in Light Water Reactors (LWR)32

Constituent of SNF

U 956

Stable FP (including Ln) 29

Pu 09

Cs amp Sr (FP) 03

I amp Tc (FP) 01

Other long-lived FP 01

MA 01

Although MA only make up 01 of fission products they are highly radiotoxic

and extremely long-lived and so it would be beneficial to separate MA from the

remaining fission products so that they can be transmutated into shorter lived

radionuclides by neutron bombardment The necessity of the separation arises from the

presence of Ln as Ln are known to be neutron scavengers or ldquoneutron poisonsrdquo 33

meaning that they have a high neutron cross section and are able to absorb neutrons

preventing transmutation of other species present

Neptunium is relatively simple to remove from the mixture of fission products

as it has a variety of oxidation states that can be utilised in the process34

However the

predominant trivalent minor actinides (MAs) Am and Cm are much more difficult to

separate from the remaining lanthanide waste due to the similarities in the chemistries

of the elements and the electrostatic nature of interactions of the hard Lewis acidic Ln3+

ions with ligands35

Much of this new research is focussed on separating Am3+

and

Cm3+

from Ln3+

55


Currently there are no MA-Ln separation techniques employed commercially

although a number of different processes are being developed particularly in the USA

and Europe with a drive to implement a working process within the next 5 years

Despite differences in the chemistry between the techniques under development all of

them use solvent extraction as the ultimate separation technique

Solvent extraction is the process of separation of two (or more) species using

two immiscible liquids (usually an organic and aqueous phase) by the use of

complexing agents to selectively move only one species between phases This may or

may not be aided by the use of a complexing agent which binds preferentially to one of

the species36

The success of this technique varies between compounds and solvent systems

and can be determined using a separation factor (SF) This is a ratio based on the

distribution ratios (D) of the elements to be separated (Equations 111 and 112)

Equation 111

Equation 112

There are a number of existing methods for removing radiotoxic elements from

fission products these are discussed over the next few sections

1341 PUREX

PUREX (Plutonium and Uranium Refinement by Extraction) is the process used

by nuclear plants that carry out reprocessing to remove U and Pu from the waste in

order to reuse it (Figure 18) Strong nitric acid (~ 4M HNO3) is used to dissolve the

waste in an aqueous phase to form hydrated nitrate complexes of the corresponding

oxides of U and Pu (Equations 113 and 114) High concentrations of acid (2-6 M) are

used to increase the solubility of the oxides

Equation 113 UO22+

+ 2NO3- (aq) rarrUO2(NO3)2xH2O

Equation 114 PuO22+

+ 2NO3- (aq) rarrPuO2(NO3)2xH2O

56

The plutonium complex is then reduced using nitrogen tetroxide (N2O4) to the

corresponding Pu4+

complex and the solution is filtered to remove any precipitates

(Equation 115)

Equation 115 PuO2(NO3)2xH2O + N2O4 rarr Pu(NO3)4xH2O

The solution is then contacted with an organic phase (kerosene) containing tri-

nbutyl phosphate (TBP) as an extracting agent (Figure 17) which forms complexes

with the U and Pu nitrate hydrates to move them into the organic phase (Equations 116

and 117)

Equation 116 UO2(NO3)2xH2O + 2TBP rarr UO2(NO3)2(TBP)2

Equation 117 PuO2(NO3)2xH2O + 2TBP rarr Pu(NO3)4(TBP)2

However Tc and Np are also extracted at this point This is a disadvantage for

the purpose of the PUREX process but is advantageous for subsequent MA-Ln

separation processes which could follow The UO22+

and NpO2+ TBP complexes are

then separated from the Pu4+

and TcO4- complexes by reduction of Pu

4+ to Pu

3+ with

hydrazine (N2H4) and extraction back into water (Equations 118 and 119)3738

Equation 118 N2H4 + H2O harr N2H5+ + OH

-

Equation 119 Pu(NO3)4(TBP)2 + N2H5+ rarr Pu(NO3)3(TBP)2 + N2H5NO3

The Pu3+

and TcO4- are then separated from each other through another

extraction cycle and then a ldquostrippingrdquo solution of nitric acid hydroxylamine and

sulphuric acid to obtain pure Pu The UO22+

and NpO2+ are also extracted back into

aqueous solution and separated from each other through another extraction cycle Pure

U is obtained by using aqueous nitric acid for stripping (back-extraction)39

The process

has been proven to work well and it is an advantage that the organic phase can be reused

after stripping However the process has a few drawbacks ndash the need for high acid

concentrations makes it less environmentally friendly the need for redox control and

less stable oxidation states makes it longer and complicated and the use of phosphorus

reagents makes the products more difficult to dispose of as phosphorus waste is not

57

incinerable and so any radioactive waste must be separated from the phosphorus before

treatment40


Figure 18 PUREX flow diagram41

1342 TRUEX

TRUEX (TRansUranic EXtraction) is an example of advanced reprocessing

(removal of MA and Ln) that is being developed in the USA The principle of the

process is to selectively remove Am and Cm (MA) and Ln from the other fission

58

products left in the raffinate after the PUREX process (Figure 110) A combination of

extractants is used carbamoylmethylphosphine oxide (CMPO) (Figure 19) and TBP (as

in the PUREX process) The benefit of the combined extractant system is that the

process is effective over a range of acidities (07-5 M HNO3) The raffinate (in nitric

acid) from the PUREX process is contacted with the extractant in an organic phase of

normal paraffinic hydrocarbon (NPH) Oxalic acid is then added to prevent the co-

extraction of zirconium (Zr) and molybdenum (Mo) with the MA An additional wash is

also performed using sodium carbonate (Na2CO3) to prevent any other fission products

from being co-extracted The extractants selectively remove the MA and Ln into the

organic phase leaving the remaining fission products in the aqueous phase The MA

and Ln are then stripped using nitric acid and can be reprocessed further as required

However a main drawback is that the lanthanides are still present with the MA so

further reprocessing is required 42



59


1343 DIAMEX

The DIAMEX (DIAMide Extraction) process is another example of advanced

reprocessing and is currently under development in France by the CEA (Commissariat agrave

lEnergie Atomique et aux Energies Alternatives) (Figure 113) It is similar to the

TRUEX process as the process selectively removes Am and Cm (MA) and Ln from the

PUREX raffinate The process is being researched using a variety of different diamides

as the extractant the most promising of which have been shown to be NNrsquo-dimethyl-

NNrsquo-dibutyl-tetradecylmalonamide (DMDBTDMA) (Figure 111) and NNrsquo-dimethyl-

NNrsquo-dioctyl-hexylethoxymalonamide (DMDOHEMA) (Figure 112)4344

The nitric

acid PUREX raffinate is contacted with the extractant in an organic phase of tetra-

propylene-hydrogenated (TPH) a synthetic branched form of dodecane45

Oxalic acid is

then added to prevent the co-extraction of Zr and Mo with the MA as in the TRUEX

process and the extractant selectively removes the MA and Ln into the organic phase

leaving behind the other fission products in the aqueous phase The MA and Ln are then

stripped using nitric acid and can be reprocessed further as required

The main benefit of this process compared to the TRUEX process is that the

organic waste only contains C H N and O as P reagents are not used so the waste can

be disposed of more easily However like the TRUEX process a main drawback is that

the lanthanides are still present with the MA so further reprocessing is required 46

Figure 111 Chemical structure of DMDBTDMA (N1N3-dibutyl-N1N3-

dimethyl-2-tetradecylmalonamide)

60

Figure 112 Chemical structure of DMDOHEMA (N1N3-dibutyl-2-(2-

(hexyloxy)ethyl)-N1N3-dimethylmalonamide)


1344 SANEX

SANEX (Selective ActiNide EXtraction) is another process being developed by

CEA and is intended to be coupled with a TRUEX or DIAMEX type process and is the

next step in the advanced reprocessing whereby the MA and Ln are separated from

each other so that the MA can be treated (Figure 117) Complexing agents such as bis-

triazinyl-pyridines BTPs and their bipyridine variants (BTBPs) (Figure 114) have been

widely studied with a more recent complexing agent tetraoctyldiglycolamide (TODGA)

(Figure 115) being studied47

The complexing agents have been found to preferentially

bind to the MA allow only the MA to be extracted into an organic phase using TBP

leaving the Ln in the aqueous phase Oxalic acid and (2-hydroxyethyl)-

61

ethylenediaminetriacetic acid (HEDTA) (Figure 116) are used to prevent the co-

extraction of any other fission products The chemistry of this process is poorly

understood however and more research is needed48

However many of these extractant

molecules suffered problems that preclude them from use in plant-scale extractions

including poor stability slow extraction kinetics the use of citric acid as a buffer and

inefficient back extraction due to high An3+ affinities

Figure 114 General chemical structure of BTPs (66-di(124-triazin-3-yl)-22-

bipyridine)

Figure 115 Chemical structure of TODGA (22-oxybis(NN-dioctylacetamide))

Figure 116 Chemical structure of HEDTA (22-((2-((carboxymethyl)(2-

hydroxyethyl)amino)ethyl)azanediyl)diacetic acid)

62


1345 i-SANEX

The innovative SANEX (or i-SANEX) process is also currently under

development at the CEA49

Essentially it is a modified DIAMEX process with selective

back extraction of Am3+

and Cm3+

from the organic phase The MA3+

and Ln3+

ions are

initially extracted from the PUREX raffinate using TODGA and then a hydrophilic

complexant that is selective for MA3+

is employed to back extract the minor actinides

from the loaded organic phase into the aqueous phase In order to retain the lanthanide

ions in the organic phase a nitrate salt is added to the stripping solution Hydrophilic

extracting agents that have been used to demonstrate this technique are DTPA

(diethylenetriaminepentaacetic acid) and the sulphonated BTP derivative 26-bis(56-

di(sulphophenyl)-124-triazin-3-yl)pyridine SFrsquos of up to 1000 are achievable in this

process50

One other option that has been suggested is to add a second stripping agent

such as HDEHP to the organic phase in order to retain the lanthanides in the organic

phase at low pH One major drawback of this process however is the limited operative

acidity range (ca pH 3) which means that buffering agents need to be added to the

aqueous phase in the back extraction step Another reprocessing concept currently under

investigation is the 1-cycle SANEX with the intention to directly extract the trivalent

actinides selectively from the PUREX raffinate A system consisting of 015 M

CyMe4BTBP and 0005 M TODGA in a mixture of 40 TPH and 60 1-octanol has

been proposed51

63

1346 GANEX

The GANEX (Grouped ActiNide EXtraction) process is relatively new and is a

complete separation process combining the principles of the PUREX and TRUEX

processes in order to separate all of the An (U Pu and MA) from the Ln and both from

the other fission products (Figure 121) A complexing agent bis-triazin-bipyridine

(BTBP) (Figure 118) and its variants (such as CyMe4-BTBP (Figure 119) and CyMe4-

BTPhen (Figure 120))52

have been tested and found to be effective in selectively

coordinating to and extracting MA high separation factors of Am3+

over Eu3+

gt 1000

have been documented In the proposed process BTBP is dissolved in cyclohexanone

(as it is soluble in this solvent and has faster extraction kinetics) and used alongside

TBP which extracts U and Pu and is stable against radiolysis and hydrolysis especially

the CyMe4 variant If proven to be successful this process would simplify reprocessing

making it much simpler however much more work is needed before this process could

become operational as co-extraction of fission products is currently a problem53

For the

most attractive candidate to date the CyMe4-BTBP extractant has been successfully

tested for the extraction of genuine actinidelanthanide feed through a 16-stage

centrifugal contactor setup with excellent recoveries for americium and curium

(gt999) but has been shown to undergo radiolytic degradation at doses that will be

encountered at the high minor actinide loadings obtained in the reprocessing of for

example fast reactor fuels The kinetics for actinide extraction with CyMe4-BTBP are

still relatively slow so the addition of a phase-transfer catalyst is necessary (eg NNprime-

dimethyl-NNprime-dioctylethylethoxymalonamide (DMDOHEMA)) if this extractant is to

be used for large- scale partitioning

Figure 118 General chemical structure of BTBPs (66rsquo-bis(124-triazin-3-yl)-22rsquo-

bipyridine)

64

Figure 119 Chemical structure of CyMe4-BTBP (66-bis(5588-tetramethyl-5678-

tetrahydrobenzo[e][124]triazin-3-yl)-22-bipyridine)

Figure 120 Chemical structure of CyMe4-BTPhen (29-bis-(124-triazin-3-yl)-110-

phenanthroline)

65


1347 TRPO

Another advanced reprocessing extraction process being developed in China is

the TRPO (TRialkyl Phosphine Oxide) process which involves the separation of all

actinides in stages to remove Np and Pu together AmCm and Ln together and isolate

U There are two processes being researched both of which use TRPO (Figure 122) as

the extractant but differ in the other reagents used One system uses TTHA (triethylene

tetramine hexaacetate) (Figure 124) as a complexing agent to selectively bind to

different actinides preferentially at different pH values to allow selective extraction

buffered by lactic acid (Figure 125) The other process uses nitric acid to extract MA

and Ln followed by oxalic acid to extract Pu and Np Both processes then use sodium

carbonate to strip the remaining U from solution (Figure 126) The main advantage of

the first system is that MA and Ln can subsequently be separated from each other using

CYANEX 301 (Figure 123) with the main disadvantage being the need for buffering

due to pH dependence The main advantage of the second system is that the separation

between components is excellent and virtually discrete but the main disadvantage is that

MA and Ln cannot be later separated from each other using CYANEX 301 due to the

high acidity of the solution54

66

Figure 124 Chemical structure of TTHA (3-(2-((2-

(bis(carboxymethyl)amino)ethyl)(carboxymethyl)amino)ethyl)-6-

(carboxymethyl)octanedioic acid)



(trialkyl phosphine oxide R = C6 ndash C8)

Figure 123 Chemical structure of

CYANEX 301 (bis(244-

trimethylpentyl)phosphinodithioic acid)

67


1348 LUCA

LUCA (Lanthaniden Und Curium Americium trennung lanthanide and curium

americium separation) is a relatively new process currently being developed in

Germany and is designed to follow the SANEX or DIAMEX processes The process

involves the selective separation of Am3+

from Cm3+

Cf3+

and Ln3+

after co-extraction

A combined extractant system of bis(chlorophenyl)dithiophosphinic acid

((ClPh)2PSSH) and tris(2-ethylhexyl)phosphate (TEHP) in isooctane and tert-butyl

benzene is used Advantages of the LUCA process include high recovery after stripping

and that the phosphinic acid is more stable to hydrolysis and radiolysis than CYANEX

301 however the phosphinic acid was found to be unstable in high HNO3

concentrations55

At present as with the majority of the MALn processes described the

exact origin of the selectivity remains unclear however it is clear that in general

simple extractant molecules are favourable

68


1349 EXAm

The EXAm (Extraction of Americium) process is another relatively new process

developed by the CEA for the extraction of only americium from a PUREX raffinate56

Americium is the main cause of heat emissions in SNF wastes and so selective removal

and reprocessing of Am is favourable for vitrified waste disposal Separation of Am3+

from Cm3+

was considered as Cm reprocessing would be difficult to implement due to

high neutron emissions which would require very thick shielding

The process uses a mixture of two extractants (DMDOHEMA and HDEHP) in

TPH from a 4-6 M HNO3 FP solution TEDGA (NNNrsquoNrsquo-tetraethyl-diglycolamide)

(Figure 128) is used as the complexing agent to selectively retain Cm3+

and Ln3+

in

solution allowing extraction of Am3+

Advantages of the process are that the use of

TEDGA over TODGA allows increased separation of Am3+

Cm3+

and TEDGA is

relatively resistant to radiolysis However the chemistry remains quite poorly

understood and separation factors are still quite low at ~25 due to the very similar

chemistry of the two metal ions57

Figure 128 Chemical structure of TEDGA (NNNrsquoNrsquo-tetraethyl-diglycolamide)

69

137 TALSPEAK

TALSPEAK (Trivalent Actinide Lanthanide Separation by Phosphorus reagent

Extraction from Aqueous Complexation) is a further effective method of advanced

reprocessing by solvent extraction The process was initially developed at Oak Ridge

National Laboratory in Tennessee USA during the 1960s and it is still being refined

The process is designed to allow the separation of MA3+

(Am3+

and Cm3+

) from

Ln3+

and yttrium (Y3+

) from the other fission products and from each other to allow MA

to be reprocessed further by transmutation Although it is still under development the

TALSPEAK process has a number of benefits over other similar processes discussed in

Section 126 The process is resistant to irradiation and allows the separation to be

carried out without the need for high acid and salt concentrations It also has added

benefits in that it has already been performed on a pilot plant scale and uses cost

effective readily available reagents58

Additionally it can be carried out using relatively

inexpensive stainless steel equipment The process is very promising despite its

potential disadvantage that it involves removing the major constituent from the minor

constituent as studies have shown the separation is effective enough for this not to be a

problem

1371 The Process

In the process the MA preferentially form complexes with an aminopolyacetic

acid chelate over the lanthanides This allows the lanthanides to be better extracted into

an organic phase by a mono-acidic organophosphate or phosphonate (Figures 132 and

134) The most effective complexing agent to date is DTPA (diethylenetriamine

pentaacetic acid) (Figure 129) in the pH 25-35 range giving relatively high SFs (~50

for Nd3+

the most difficult to extract Ln3+

ion) and the most effective extracting agents

are HDEHP (di(2-ethylhexyl)phosphoric acid) (Figure 130) and HEH[ϕP] (2-

ethylhexyl phenyl phosphonic acid) (Figure 131) The extraction can be carried out

without the use of a complexing agent although the separation is not as discrete and is

significantly enhanced by the addition of an aminopolyacetic acid such as DTPA

Without DTPA Eu3+

Am3+

separation factors using 03 M HDEHP are around 40 59

whereas SF ~90 can be achieved when the complexing agent is used with the extractant

Other aminopolyacetic acids have been tested such as TTHA and EDTA but are not as

effective or tend to be less soluble60

70

Figure 129 Chemical structure of DTPA (2222-

((((carboxymethyl)azanediyl)bis(ethane-21-diyl))bis(azanetriyl))tetraacetic acid)

TALSPEAK Process

1 The fission product mixture (1 M) is dissolved in a carboxylic acid which acts

as a buffer and a solubiliser for the complexing agent lactic acid is often used

for this (Figure 132) Lactic acid (pKa 386)61

has been found to be the best

buffer for the process as it gives the best phase separation Nitrate may be

present from the original raffinate but this has been found not to decrease

separation

2 The solution is ldquoscrubbedrdquo with a mixture of Na5DTPA (01 M) in the same

carboxylic acid (1 M) at pH 36 ndash 38 The DTPA5-

complexes to the MA3+

and

Ln3+

but binds more strongly to the MA3+

This pH range is the optimum pH for

DTPA5-

activity as it complexes more strongly at higher pH values but

separation is better in more acidic conditions


HDEHP (bis(2-ethylhexyl) hydrogen

phosphate)


HEH[ϕP] ((2-(2-

ethylhexyl)phenyl)phosphonic acid)

71

3 The extractant is dilute HDEHP (05 M) in a hydrocarbon solution such as

DIPB (diisopropyl benzene found to give the best separation) which is then

contacted with the aqueous solution containing the LnMA[DTPA]2-

The Ln3+

ions are extracted into the organic phase by the phosphate causing dissociation

of the DTPA5-

and leaving the free DTPA5-

in the aqueous solution The

MA[DTPA]2-

complexes remain in the aqueous solution as DTPA5-

is bound

strongly enough to MA3+

to prevent the complexes from dissociating HEH[ϕP]

gives a better extraction although it makes stripping more difficult

4 After the Ln3+

ions are removed a second scrub is carried out at lower pH (15)

and a lower concentration of the complexing agent (005 M Na5DTPA) in lactic

acid (1 M) in order to extract the MA3+

The lower pH increases the extraction

rate as the DTPA5-

binds less strongly to the MA3+

allowing them to be

extracted more easily at the phase boundary where DTPA5-

dissociates The

phosphate (03 M HDEHP) is dissolved in n-dodecane (a more favourable

diluent) for the second extraction to remove the MA3+

into the organic phase

The use of n-dodecane was found to give better extraction but poorer

separation If Ln3+

and Y3+

are the only fission products present in the original

raffinate solution the MA3+

can be recovered by precipitation with oxalate from

the raffinate

5 Stripping is then carried out using 1 M HNO3 Nitric acid prevents the use of

corrosive chlorides This process can also be used to extract Cf3+

and Es3+

but it

has been found that more concentrated acid is needed for heavier actinides


72

Figure 133 The solvent extraction process used in TALSPEAK Step 1 Binding of

DTPA to M3+

in the aqueous phase at pH 36 buffered by lactic acid Step 2 Selective

extraction of Ln3+

into the organic phase by HDEHP from the aqueous phase due to

preferential binding of DTPA to MA3+

Additional Notes on the Process

Initial extraction data for the process reported by Weaver et al in 1964 was

obtained by adding isotopic tracers to the aqueous solutions contacting them with the

organic phase performing the separation and measuring the activity by scintillation

counting with a γ-detector Extractions were all repeated 2-3 times to verify the results

and the contact time was 20 minutes which was much longer than necessary

Extractions performed using Na5DTPA and H5DTPA were found to give the same

results at the same pH values although pH adjustment was needed as Na5DTPA is more

alkaline than H5DTPA but H5DTPA is much less soluble The extraction of heavier

lanthanides was found to be slower but did not affect the separation Increasing the

concentration of HDEHP was found to give better separation but made the initial

equilibration time too long and increasing the concentration of DTPA decreased the

separation (Figure 134)

1 2

73

Figure 134 Effect of Na5DTPA concentration on distribution ratios of MA3+

and Ln3+

in TALSPEAK process using 1 M lactate buffer and 03 M HDEHP in DIPB extractant

60

The process is based on the preferential binding of the complexant to the

trivalent actinides over lanthanides Initially this was thought to be due to the fact that

An3+

binding is more covalent than Ln3+

binding However this was found not to be the

sole reason and it is understood that the organic ligand plays a role in the selectivity

The chemistry of the complexation of the ions with the ligand is not yet fully

understood and much work is needed to gain an insight into this complicated

chemistry62

74



The necessity of reprocessing has arisen from increasing awareness and concern

for the environment in addition to the potential of maximising finite resources whilst

minimising proliferation There are a number of different processes currently under

development none of which have yet been implemented on a commercial scale except

for the PUREX process

The principles of all these process are often very similar although extraction

techniques and reagents vary somewhat There are a number of factors which must be

considered when developing a suitable solvent extraction process for SNF reprocessing

including the ease of stripping (back-extraction) the need for low volatility non-

flammable solvents the potential of the process to be continuous how to minimise

waste production the resistance of the process to radiolysis and degradation

practicality and efficiency of the process and the economic viability63

While some of the chemistry is understood such as the redox chemistry in the

PUREX process much of it is not thus limiting the potential to develop an efficient

process The sheer complexity of the waste content makes partitioning very difficult

and without a full understanding of the chemistry involved in the processes designing

75

an effective working process will be very challenging All of the processes currently

under development have advantages and disadvantages but all are ultimately heading

towards the same goal separation of the actinides from the lanthanides in order allow

the transmutation of the actinides into shorter lived radionuclides for the purpose of

reducing the long-term radiotoxicity of the waste and the volume of waste building up

in storage


numerous advantages particularly its relative resistance to irradiation and ability to be

carried out without the need for high reagent concentrations Additionally it gives

separation factors of ~50-100 comparable to the SANEX process which uses BTP one

of the most effective complexing agents However its main disadvantage is the poor

understanding of the separation mechanisms and complexation chemistry surrounding

it The main focus of research here will be the TALSPEAK process with a view to

improving the understanding of this chemistry and modifying the process to improve its

practicality


Recent studies have shown that complexants with soft donor atoms compared to

oxygen (such as N or S) can be used to separate the MA from Ln6465

Initial research in

this area was carried out by our collaborators at Idaho National Lab using amino acids

as a potential buffer and soft donor which if proven to be successful would be able to

eliminate the need for the separate complexing agent and buffer simplifying the process

if amino acids were found to preferentially bind to the MA66

Another benefit to this

change would be the scope for carrying out the process at a lower pH due to the lower

pKa values of the carboxylic acid groups of the amino acids than on DTPA enabling

the system to be buffered to pH 1-2 rather than ~35 Lower pH values are preferred by

industry as higher acid concentrations are easier to control on a large scale pH control

is essential for the distribution ratios for the separation and there is a strong correlation

between the two Low pH values have been found to increase D however DTPA

protonates and precipitates out of the solution at the lowest values The use of amino

acids in place of the complexing agent would allow a lower pH to be used as they would

not fully protonate increasing the SF and making the process more efficient as binding

constants and ligand affinities would be higher To this end several avenues of research

have been explored

76

Chapter 2 presents initial studies carried out using amino acids in a TALSPEAK

system the interaction of amino acids with lanthanide and actinide ions and their

complexes in solution and the susceptibility of amino acid systems to radiolysis

Chapter 3 discusses work carried out at the INL on an L-alanine-buffered

system optimisation of the alanine system at pH 2 in order to maximise separation

potential and the consideration of other amino acid buffers over a range of pH values

Chapter 4 is focussed on an L-glutathione (GSH) buffered system GSH is a

tripeptide showing promise for an improved TALSPEAK system the next step after

research using single amino acids Data was initially obtained via solvent extraction in

order to investigate the separation ability of GSH and conditions were then optimised in

order to achieve maximum separation Interaction of the buffer with various

components in solution including lanthanide ions was probed using various techniques

including luminescence spectroscopy which was also used in determining the

susceptibility of the buffer to -radiolysis

Chapter 5 details the synthesis of amino acid appended DTPA ligands and their

complexation with lanthanide ions as well as their extraction and separation abilities

under different conditions along with radiolysis resistant investigations

77

1 S Cotton Lanthanide and Actinide Chemistry ed D Woolins R Crabtree D

Atwood and G Meyer John Wiley amp Sons Chichester UK 2006 1 1-7

2 C H Evans Episodes from the History of the Rare Earth Elements Kluwer

Academic Publishers Dordrecht Netherlands 1996

3 S Cotton Education in Chemistry 1999 36 4 96 WR Wilmarth RG Haire JP

Young DW Ramey JR Peterson J Less Common Metals 1988 141 275

4 LR Morss NM Edelstein and J Fuger The Chemistry of the Actindie and

Transactinide Elements Springer The Netherlands 4th edn 2010

5 AP Jones F Wall CT Williams Rare Earth Minerals Chemistry Origin and Ore

Deposits ed AP Jones F Wall and CT Williams Chapman and Hall London UK

1966 1 6-10

6 JJ Katz and GT Seaborg The Chemistry of The Actinide Elements Methuen amp Co

Ltd The Pitman Press Great Britain 1957

7 N Kaltsoyannis and P Scott The f elements ed R G Compton S G Davies J

Evans and L F Gladden Oxford University Press United States 1st edn 1999

8 Greenwood NN and Earnshaw A Chemistry of the Elements Butterworth-

Heinemann Great Britain 2nd edn1997

9 MB Jones AJ Gaunt Chem Rev 2012 DOI 101021cr300198m

10 L Natrajan F Burdet J Peacutecaut M Mazzanti J Am Chem Soc 2006 128 7152

11 C Fillaux D Guillaumont J-C Berthet R Copping D Shuh T Tyliszczak C

Den Auwer Phys Chem Chem Phys 2010 12 14253

12 HC Aspinall Chemistry of the f-block Elements ed D Phillips P OrsquoBrien and S

Roberts Gordon and Breach Science Publishers Singapore 2001 vol 5

13 F Gendron K Sharkas and J Autschbach J Phys Chem Lett 2015 6 2183-

2188

14 VBE Thomsen J Chem Educ 1995 72 (7) 616-618

15 Dr Louise Natrajan School of Chemistry The University of Manchester

16 JP Leonard CB Nolan F Stomeo and T Gunnlaugsson Topics in Current

Chemistry 2007 vol 281 pp1-43

17 Y Ma and Y Wang Co-ord Chem Rev 2010 254 972-990

18 LS Natrajan AN Swinburne MB Andrews S Randall and SL Heath Coordin

Chem Rev 2014 266-267 171-193

19 A Bettencourt-Dias Dalton Trans 2007 2229-2241

20 E Hashem AN Swinburne C Schulzke JD Kelly RC Evans JA Platts A

Kerridge LS Natrajan and RJ Baker RSC Adv 2013 3 4350

78

21 C Turro PK Fu and PM Bradley Met Ions Biol Syst 2003 40 323-353


23 I Billard and G Geipel Springer Ser Fluoresc 2008 5 465-492

24 A Beeby IM Clarkson RS Dickins S Faulkner D Parker L Royle AS de

Sousa JAG Williams and M Woods J Chem Soc Perkin Trans 2 1999 493-504

25 WD Horrocks and DR Sudnick J Am Chem Soc 1979 101 334

26 RM Supkowski and WD Horrocks Inorg Chim Acta 2002 340 44-48

27 Dummiesreg Nuclear Fission Basics httpwwwdummiescomhow-

tocontentnuclear-fission-basicshtml 2015

28 PE Hodgson Nuclear Power Energy and the Environment Imperial College Press

Great Britain 1999

29 P Dyck and MJ Crijns Rising Needs IAEA Bulletin 1998 40 1

30 World Nuclear Association The Nuclear Fuel Cycle httpwwwworld-

nuclearorginfoinf03html 2011

31 Nuclearmatterscouk Re-use of Plutonium as MOX Fuel

httpnuclearmatterscouk201202re-use-of-plutonium-as-mox-fuel 2012

32 World Nuclear Association Processing of Used Nuclear Fuel 2012

httpwwwworld-nuclearorginfoinf69htmla

33 United States Nuclear Regulatory Commission Neutron poison httpwwwnrcgov

2012

34 K L Nash Solvent Extraction and Ion Exchange 1993 114 729-768

35 M P Jensen L R Morss J V Beitz and D D Ensor Journal of Alloys and

Compounds 2000 303-304 137-141

36 Advanced Separation Techniques for Nuclear Fuel Reprocessing and Radioactive

Waste Treatment ed KL Nash and GL Lumetta Woodhead Publishing 1st edn

Cambridge UK 2011

37 CS Dileep Poonam Jagasia PS Dhami PV Achuthan AD Moorthy U

Jambunathan SK Munshi PK Dey and BS Tomar BARC Newsletter 2007 285

130-134

38 H Schmieder G Petrich and A Hollmann J Inorg Nucl Chem 1981 43 (12)

3373-3376

39 SC Tripathi and A Ramanujam Sep Sci and Technol 2003 38 2307

40 G Thiollet and C Musikas Solv Extr Ion Exch 1989 7 813

41 GL De Poorter and CK Rofer-De Poorter 720872 1976 US Pat 4080273 1978

79

42 EP Horwitz DC Kalina H Diamond GF Vandegrift and WW Schulz Solv

Extr Ion Exch 1985 31 75-109

43 A Banc P Bauduin and O Diat Chem Phys Lett 2010 494 (4-6) 301-305

44 J Muller L Bethon N Zorz and J-P Simonin Proceedings of the First ACSEPT

International Workshop 2010

45 C Brassier-Lecarme P Baron JL Chevalier and C Madic Hydrometallurgy

1997 47 57-67

46 O Courson R Malmbeck G Pagliosa K Romer B Satmark J-P Glatz P Baron

and C Madic Radiochim Acta 2000 88 865-871

47 M Sypula A Wilden C Schreinemachers and G Modolo Proceedings of the First

ACSEPT International Workshop 2010

48 C Hill L Berthon P Bros J-P Dancausse and D Guillaneux Nuclear Energy

Agency 7th Information Exchange Meeting Session II 2002

49 S Bourg C Hill C Caravaca C Rhodes C Ekberg R Taylor A Geist G

Modolo L Cassayre G de Angelis A Espartero S Bouvet N Ouvrier Nucl Eng

Des 2011 241 3427 G Modolo A Wilden A Geist D Magnusson R Malmbeck

Radiochim Acta 2012 100 715

50 A Geist U Muumlllich D Magnusson P Kaden G Modolo A Wilden T Zevaco

Solv Extr Ion Exchange 2012 30 433

51 A Wilden C Schreinemachers M Sypula G Modolo Solv Extr Ion Exch 2011

29 190

52 FW Lewis LM Harwood MJ Hudson MGB Drew V Hubscher-Bruder V

Videva F Arnaud-Neu K Stamberg and S Vyas Inorg Chem 2013 52 4993-5005

53 E Aneheim C Ekberg A Fermvik M R St J Foreman T Retegan and G

Skarnemark Solv Extr Ion Exch 2010 284 437-458

54 M Wei X Liu and J Chen J Radioanal Nucl Chem 2012 291 717-723

55 G Modolo P Kluxen A Geist Radiochim Acta 2010 98 193

56 C Rostaing C Poinssot D Warin P Baron and B Lorrain Procedia Chem 2012

7 349-357

57 S Chapron C Marie G Arrachart M Miguirditchian and S Pellet-Rostaing Solv

Extraction and Ion Exchange 2015 33 236-248

58 M Milsson and K L Nash Solvent Extraction and Ion Exchange 2009 273 354-

377

59 G Lumetta AV Gelis and GF Vandegrift Solv Extraction and Ion Exchange

2010 28 3 287-312

80

60 B Weaver and T A Kappelmann Talspeak A new method of separating americium

and curium from the lanthanides by extraction from an aqueous solution of an

aminopolyacetic acid complex with a monoacidic organophosphate or phosphonate

Oak Ridge National Laboratory 1964 1-60

61 K W Raymond General Organic and Biological Chemistry An Integrated

Approach John Wiley amp Sons USA 3rd edn 2010 7 253

62 L Karmazin M Mazzanti C Gateau C Hill and J Peacutecaut Chem Commun 2002

2892-2893

63 KL Nash Actinide Solution Chemistry Proceedings of the Eighth Actinide

Conference Actinides 2005

64 M P Jensen and A H Bond J Am Chem Soc 2002 124 9870-9877

65 L R Martin B J Mincher and N C Schmitt J Radioanal Nucl Chem 2009

282 523-526

66 S Oumlzҫubukҫu K Mandal S Wegner M P Jensen and C He Inorg Chem 2011

50 7937-7939

81

2 COMPLEXATION STUDIES OF Ln amp An WITH DTPA AND BUFFERS

UNDER TALSPEAK CONDITIONS

DTPA (diethylenetriaminepentaacetic acid) is an amino polycarboxylic acid

used to act as a holdback reagent in the TALSPEAK process (Trivalent Actinide

Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Complexation)

an advanced reprocessing technique currently being developed in the USA (Section

137) DTPA is the chelating agent used as it has been shown to complex more strongly

to trivalent minor actinide ions (MA3+

) than lanthanide ions (Ln3+

) in aqueous solution

allowing selective extraction of lanthanides into an organic phase by organophosphate

HDEHP (di-(2ethylhexyl)phosphoric acid) to separate the two components


It is widely known that DTPA ligands bind very well to metal ions in aqueous

media It is commonly used to extract heavy metals from soils for environmental

reasons1 and to treat heavy metal poisoning through its ability to chelate to heavy

metals making them more water soluble and able to be removed from the body

naturally by excretion2 Lanthanide DTPA complexes have been well established

although there is actually very little structural data available on them Most literature

references to lanthanide DTPA complexes discuss their use as MRI contrast agents the

most common choice being Gd-DTPA3 Other reported applications of DTPA-based

lanthanide complexes are for use as biological luminescent probes particularly with Eu4

and Tb5 Due to the highly hygroscopic nature of Ln-DTPA complexes solid state

structural analysis has only been reported in two instances as molecular structures

determined by X-ray absorption spectroscopy (XAS) one for Gd(III)-DTPA (Figure

21) and one for Eu(II)-DTPA6 Most solution state structural analysis for lanthanide

DTPA complexes has been carried out recently in order to better understand MALn

separation and TALSPEAK chemistry The only literature available on An-DTPA

complexes is related to separations chemistry except for actinium-DTPA used in

radiotherapy7

82

Figure 21 XAS molecular structure of Gd(III)-DTPA8


Reports on the formation of trivalent actinide complexes with DTPA detail that

the stability of AnDTPA2-

complexes (the dominant DTPA species present at pH 36

which is the pH currently used in the TALSPEAK process) is greater than the stability

of LnDTPA2-

complexes allowing the selective extraction on Ln3+

to take place For

LnDTPA2-

complexes stability constants range from log β = 1948 for La increasing

across the series up to log β = 2283 for Dy (with a slight dip at Gd) decreasing slightly

for the heavier Ln3+

complexes

Stability constants in the literature for AnDTPA2-

have been determined by a

range of techniques including TRLFS CE-ICP-MS spectrophotometry and solvent

extraction and range from log β = 2257 to 2403 for AmDTPA2-

and from log β = 2238

- 2348 for CmDTPA2-

at an ionic strength (I) of 01 M However there is some dispute

on whether AnHDTPA- complexes are also present in solution and this needs to be

accounted for when calculating stability constants as some of these values have been

determined with and some without consideration of AnHDTPA-9101112

Studies conducted by Martin et al determined stability constants of log β =

2219 - 2085 for CmDTPA2-

at I = 1 M over a temperature range of 10-70 degC

compared to log β = 2131 - 2033 for EuDTPA2-

over the same temperature range The

complex EuHDTPA- was found to have a stability constant of log β = 227 - 210 under

TALSPEAK conditions Europium(III)is used as a standard comparison to Am3+

Cm3+

due to the close similarity in chemistry between the elements as a result of their

electronic structures This data clearly shows that the Cm3+

has a higher binding

83

strength to DTPA5-

than Eu3+

The greater exothermic enthalpy of complexation of

CmDTPA2-

than EuDTPA2-

(-407 kJ mol-1

vs -336 kJ mol-1

) determined by

microcalorimetry indicated stronger covalent bonding of Cm3+

to DTPA5-

than Eu3+

Luminescence spectroscopy carried out in support of these studies found that

CmDTPA2-

has a shorter luminescence lifetime than EuDTPA2-

(268 micros in H2O 815 micros

in D2O for Cm3+

cf 630 micros in H2O 6200 micros in D2O for Eu3+

) This along with the

biexponential decay pattern indicating the presence of two species for Cm3+

was

attributed to faster exchange between Eu3+

and the ligandsolvent than for Cm3+

suggesting that the exchange for Eu3+

is not distinguishable on the luminescence

timescale and therefore less susceptible to the associated quenching effects This may be

due to the more ionic bonding of Eu3+

to the ligand

The pKa for the protonation of MDTPA2-

to MHDTPA- (M = metal ion) is 227

for Eu and 025 for Cm indicating that CmHDTPA- is only likely to be present in

solutions of very low pH (pH ltlt 1) It was hypothesised that the presence of

LnHDTPA- facilitates the exchange between ligand and solvent explaining the

observed difference in luminescence lifetime data consistent with stronger

complexation of MA3+

to DTPA and slower kinetics of MA3+

extraction as the

MDTPA2-

is less likely to dissociate13

212 Co-ordination Chemistry of Ln-DTPA and An-DTPA Complexes

It is known that Ln3+

ions co-ordinate to DTPA5-

in aqueous solution at pH 36

through the 5 deprotonated carboxylate groups (COO-) on the molecule and through the

three nitrogen atoms on the DTPA backbone forming an octadentate complex with one

water molecule in its inner hydration sphere giving the Eu3+

ion a co-ordination number

of 9 in the shape of a distorted capped square antiprism This is also the case for the

LnHDTPA- species


84

The co-ordination mode of DTPA5-

to MA3+

is the same as for Ln3+

octadentate

(Figure 21) with a co-ordination number of 9 due to 1 water molecule bound to the

metal ion Hydration numbers of 2 have been reported for Cm-DTPA complexes but

have been found not to be stable14

DFT optimisation of CmDTPA2-

and EuDTPA2-

structures conducted by Martin

et al found that the M-O bond lengths were similar for both metal ions but that the M-

N bond lengths were shorter for Cm3+

than Eu3+

(by 004-008 Aring) Considering that

Cm3+

has a larger ionic radius than Eu3+

this suggests that Cm3+

binds more strongly to

the intermediate N donors on the DTPA molecule Further optimisations showed that

significant changes in bond lengths upon protonation of MDTPA2-

to MHDTPA-

indicated that M-N interactions are weakened to a greater extent for Cm3+

than Eu3+

so

that MHDTPA- is less likely to form for Cm

3+ in solution than Eu

3+ This data is

consistent with the pKa data for the complexes (Section 211)


As a first experiment (in order to verify the experimental procedures for

subsequent studies) the complex [Eu(DTPA)H2O]2-

was formed from europium nitrate

(1 mM) and Na5DTPA (005 M) in H2O and D2O at pH 36 and characterised by 1H

NMR spectroscopy (for the complex in D2O) and luminescence spectroscopy (D2O and

H2O)


1H NMR spectra are difficult to fully assign for Ln

3+ DTPA complexes due to

both the paramagnetic nature of the ions and the (fast) chemical exchange of the CH2

carboxylate and ethylene diamine backbone protons which results in significant

spectral broadening However complex formation can be verified at lower temperatures

(here 5 degC) where this conformational exchange is slowed down so the paramagnetic

broadening and shifting of the CH2 DTPA proton resonances can be observed in the 1H

NMR spectrum (Figure 23) by comparison with uncomplexed DTPA (Figures 24a-c)

85

EUDTPAESP

15 10 5 0 -5 -10 -15 -20

Chemical Shift (ppm)

0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

152

8

99

196

6

88

4

53

7

42

536

033

528

7

15

8

-01

1

-16

1

-40

6

-57

3-6

33

-105

3

-126

8

-148

3

-170

2

-184

7


2- in D2O at 278 K at pD = 36

DTPA pH71resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

199100215418

DEUTERIUM OXIDE

Water

38

1

34

033

833

632

8

30

630

530

3

a

86

DTPA pH361resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

204206100421

Water

47

647

5

38

5

35

634

634

434

3

31

531

431

2

DTPA pH21resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

202199100406

Water

47

5 46

9

39

0

35

4

34

033

933

7

31

130

930

8

Figure 24 1H NMR spectra of DTPA in D2O at 278 K at varying pD a) pD 7

[DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]


Emission spectra were recorded for Eu

3+ (1 mM) with and without DTPA

5- (005

M) present in aqueous solution (Figure 25) following 397 nm excitation directly into

the 5L6 f-f absorption band

15 The formation of [Eu(DTPA)]

2- can be observed by the

splitting of the peaks in the emission spectrum of the complex compared to the free

Eu3+

(aq) representing the 5D0 rarr

7FJ transitions where J = 0 1 2 3 and 4 This is due to

crystal field splitting caused by the ligand and is indicative of strong binding of the

ligand to Eu3+

ion at pH 361617

The emission intensity is also significantly enhanced

upon the complexation of Eu3+

to DTPA5-

as the chelating ligand forms an octadentate

b

c

87

complex significantly lowering the degree of quenching of the emission by surrounding

solvent molecules



in D2O at pD 36

Additionally the luminescence lifetimes of the free Eu3+

(aq) and the

[Eu(DTPA)]2-

complex were measured in D2O and H2O This allows calculation of q

which represents the number of bound solvent molecules in the inner hydration sphere

of the metal ion The original Horrocks equation18

(Equation 19) and modified

Horrocks equation1920

for q lt 2 (Equation 110) are shown below

Equation 21

Equation 22





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+

The q values can be effectively determined from solutions of water and

methanol For the original Horrocksrsquo equation A = 105 for Eu3+

and A = 42 for Tb3+

and for the modified Horrocksrsquo equation (when q lt 2 ) A = 12 ms and B = (025 ndash

0

2

4

6

8

10

12

14

16

18

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

[Eu(DTPA)]2-

Eu3+

5D0 rarr 7F0

5D0 rarr 7F1

5D0 rarr 7F2

5D0 rarr 7F3

5D0 rarr 7F4

88

0075x) ms-1

(where x = the number of exchangeable N-H oscillators) for Eu3+

and A =

5 ms and B = 006 ms-1

for Tb3+

The q value was found to be 9 for Eu3+

(aq) suggesting that the Eu3+

ion is

surrounded by 9 solvent molecules forming [Eu(H2O)9]3+

in aqueous solution as

expected For [Eu(DTPA)]2-

formed at pH 36 q was found to be 14 plusmn 02 showing that

only 1 water molecule is bound to the metal ion This compares well to the literature

values reported at pH 7 where the lifetimes are similar and q = 1121


The aminopolycarboxylate DTPA5-

chelates even more strongly to An3+

ions

than Ln3+

ions Preliminary 1H NMR and luminescence analyses were carried out by

Louise Natrajan at KIT-INE in Karlsruhe Germany on Am3+

and Cm3+

complexation

with DTPA as part of the FP7 EURACT-NMR scheme (Scheme 21)

Scheme 21 Complexation of DTPA to Am3+

and Cm3+


The complex [Am(DTPA)xH2O]2-

was formed and analysed by 1H NMR in a

41 ratio of MeODD2O with an additional drop of NaOD to ensure complex formation

from a dried acidic americium nitrate stock salt and Na5DTPA The spectra were taken

over a temperature range of 210-365 K at ~ pD 3 (Figure 26) Note here that the exact

pD of the solution could not be accurately measured due to the high specific activity of

the 241

Am isotope used From the spectrum it can be seen that at pD 3 there is a DTPA

complex formed and that at higher temperatures there are some dynamic exchange

processes occurring as the resonances become broader and the spectrum becomes

simpler This is most likely due to conformational changes in the DTPA ligand

(movement of the carboxylates and the ethylene bridge protons analogous to DOTA

and DO3A derivatives)22

The Am3+

ion is essentially diamagnetic as it has a 7F0 ground state and the

magnetic moment is calculated as 0 based on the Russell Saunders coupling scheme

89

The same is true for the isoelectronic lanthanide analogue Eu3+

but in this ion

significant paramagnetism is induced at room temperature due to low-lying energy

levels that are thermally populated according to the Boltzmann distribution Thermal

mixing of J states induces a paramagnetic shift but in the case of Am3+

the second J

level lies much higher in energy (~ 4000 cm-1

higher) so may only be populated and

induce a paramagnetic shifting of proton resonances at higher temperatures2324

Indeed

a slight shift of the proton resonances with temperature is observed for

[Am(DTPA)xH2O]2-

potentially indicating a small contribution of the Am3+

7F1 excited

state to the chemical shift of the proton resonances


2- in 41 vv MeODD2O with

NaOD over a temperature range at pH 3


Emission spectra were recorded for solutions of

243Cm

3+ (015 microM Cm

3+ in 32

mM HClO4 diluted to 1 mL with H2O) with and without Na5DTPA (02 M) present in

aqueous solution following direct excitation at 3966 nm into the f-f absorption band of

Cm3+

(Figure 27) The formation of [Cm(DTPA)]2-

can be observed by the immediate

formation of a new red shifted emission band at 607 nm attributed to the 6D72

8S72

transition in the complex compared to that in free Cm

3+(aq)

at 593 nm The f-f transitions

in Cm3+

are much more sensitive to the coordination environment than Ln3+

due to more

210 K

265 K

300 K

365 K

90

spin orbit coupling and the fact the 5f orbitals are more spatially diffuse than the 4f

orbitals resulting in a much greater difference in emission spectra upon complexation

for actinides than lanthanides


and [Cm(DTPA)]2-

in perchloric acid at pH 3

by direct excitation with a NdYAG pumped dye laser at 3966 nm

Similarly to Eu3+

the inner hydration sphere of the free Cm3+

ion is known to

contain 9 water molecules25

In 1998 Kimura and Choppin developed a modified

version of the Horrocks equation in order to allow q to be calculated from aqueousnon-

aqueous solvent mixtures (Equation 23)26

Equation 23

The lifetime of the [Cm(DTPA)]2-

complex in H2O is 510 micros and is significantly

longer than that of the aqua ion which is determined as 68 micros The radiative lifetime of

the complex can be directly inserted into this equation and indicates that there are 16

water molecules (between 1 and 2) co-ordinated to the metal ion again showing the

formation of an octadentate complex with DTPA ligand analogously to Eu3+


and Ln-DTPA Complexes



A lactic acidlactate buffer is used in the TALSPEAK process to buffer the

system to pH 36 Lactate (Lac) is known to co-ordinate to M3+

ions27

to form

40

45

50

55

60

65

70

75

80

570 590 610 630

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

Cm3+(aq)

[Cm(DTPA)]2-

91

M3+

(CH3CH(OH)COO-)3 Equations 24a-c show the formation of Eu

3+-lactate

complexes

Equation 24a-c

(a)

(b)

(c)

Stability constants for each of the species formed in Equations 24a-c were

determined by Martin et al over a temperature range of 0-70 degC Log β values were

found to be 290-281 for Eu(Lac)2+

log β = 490-449 for Eu(Lac)2+ and log β = 624-

633 for Eu(Lac)3 Luminescence spectroscopy of Eu-lactate formation showed that as

the concentration of lactate was increased from 0 mM to 73 mM the emission intensity

of the J=2 peak (5D0 rarr

7F2 transition) at 615-620 nm increased but the J=1 peak (

5D0 rarr

7F1 transition) at 590-600 nm was not significantly affected changing the J=1J=2 peak

ratio suggesting that the co-ordination mode of the lactate to the Eu3+

ion changes as a

function of lactate concentration as the J=1 peak is a magnetic dipole transition which is

insensitive to the co-ordination of the ion (Figure 28)28

Figure 28 Emission spectrum of Eu-lactate as a function of lactate concentration28

The luminescence lifetimes of Eu3+

in water also increased as the lactate

concentration was increased indicating that the number of water molecules directly co-

ordinated to the metal ion decreases from ~9 to ~5 due to complexation with lactate

Luminescence and thermodynamic data suggest that lactate co-ordinates in a bidentate

92

mode to Ln3+

ions through the deprotonated carboxylate group and also through the α-

hydroxyl group (Figure 29) making Ln-lactate complexes more stable than simple

monocarboxylates with monodentate co-ordination28


28

The interaction of lactate ions with metal-DTPA complexes is less well

understood It is considered that there is an exchange between the Ln3+

ion and the

lactate and DTPA ligands The concentration of lactate has been shown by Nash et al to

affect the complexation and dissociation of [Ln(DTPA)]2-

however it is not understood

whether this is due to the changing pH with lactate concentration since extraction in the

TALSPEAK process is heavily dependent on pH29

TALSPEAK extractions using

lactate without DTPA show poor separation of Ln3+

over Am3+

DTPA is required to

achieve separation of MA3+

from Ln3+

as lactic acid acts only as a buffer and not a

holdback reagent

Research has shown previously that binary complexes are dominant in the

TALSPEAK process chiefly in the form of MDTPA2-

and M(Lac)n3-n

Studies carried

out using spectrophotometry luminescence spectroscopy and thermometric

experiments have shown that ternary M3+

-DTPA-lactate complexes with lactate co-

ordinated directly to the metal centre are only present in very small quantities and so

will have negligible effect on metal separation However it is possible that outer sphere

ternary M3+

-DTPA-lactate complexes may form where the lactate interacts with the

DTPA molecule although it is expected these would also be present only in minor

quantities and so would also have negligible effect on metal separation30



The potential of using amino acids as a combined buffer and soft donor was

considered as it was thought that the increased number of softer donors on amino acids

93

compared to lactate may remove the need for the separate buffer and DTPA holdback

reagent if amino acids were found to preferentially bind to MA3+

in solution There have

been few studies on the interaction of amino acids with lanthanide ions and none with

actinide ions or with DTPA Stability constants for amino acids with lanthanide ions31

can be found in the literature and like stability of lactate complexes with Ln3+

ions32

generally tend to increase across the lanthanide series from La-Lu as the Lewis acidity

of the metal ions increases The values are close to the stability constants for Ln-lactate

complexes averaging at around 5-6 depending on the metal ion and amino acid Log β

values for La-Sm with glycine range from 532-584 and with L-alanine log β = 582-

668


and [M(DTPA)]2-

Initial studies in this area considered the interaction of various amino acids and

lactate with lanthanide ions in TALSPEAK systems The amino acids glycine L-alanine

and L-serine (Figure 210) were chosen to begin this research due to their similarity in

molecular structure to lactate and good solubility in water

Figure 210 Chemical structures of L-alanine (top) glycine (bottom left) and L-serine

(bottom right)

251 1H NMR Studies on Buffer Interactions

L-alanine (1 M) was added to Eu(NO3)3 (10 mM) in D2O and analysed by

1H

NMR spectroscopy (Figure 211) The spectrum shows that L-alanine complexes

weakly with the metal ion as there is minimal paramagnetic line broadening and only

slight shifting of the proton resonances from that of L-alanine itself (Figure 212)

94

New Eu Ala0011resp

55 50 45 40 35 30 25 20 15 10 05 0


0

005

010

015

Norm

alized Inte

nsity

310100

CH3

CH

Water

47

147

1

35

5

12

712

6

Figure 211 1H NMR spectrum of Eu(NO3)3xH2O (10 mM) with L-alanine in D2O at

278 K

Ala1resp

55 50 45 40 35 30 25 20 15 10 05 0


0

01

02

03

04

05

06

07

08

09

10

Norm

alized Inte

nsity

336100

CH3

CH

Water

36

536

336

2

13

3


95

The interaction of L-alanine (1 M) with [Eu(DTPA)]2-

(10 mM) in D2O was also

investigated by 1H NMR spectroscopy (Figure 213) This spectrum shows that the L-

alanine does not bind to the europium DTPA complex on the experimental timescale as

there is no paramagnetic broadening or shifting of the amino acid peaks and the ligand

is present as uncomplexed ligand

EuDTPA Ala1esp

15 10 5 0 -5 -10 -15 -20


0005

0010

0015

0020

0025

0030

0035

Norm

alized Inte

nsity

150

5 96

892

185

2

75

4

50

4

39

533

231

625

8

14

6

05

0

-13

1

-44

2

-63

3-6

86

-108

2

-127

6

-143

1

-169

0

-183

9


2- (10 mM) with L-alanine (1 M) in D2O

at 278 K



Luminescence studies on a [Tb(DTPA)]2-

(1 mM) complex in the presence of

the amino acid L-phenylalanine (05 M) (Figure 215) at pH 3 were initially carried out

in order to determine if sensitised emission occurs whereby energy would be

transferred from the phenyl chromophore of the amino acid to the metal ion This could

potentially occur if the amino acid was in close proximity (ie bound) to the metal ion

and would give some indication into the interaction between the amino acid and the

metal ion However sensitised emission was found not to occur as when the complex

was excited in the region of the phenyl chromophore (250 nm) no emission occurred

When excited directly into the f-f region of the Tb3+

complex at 379 nm there was a

slight decrease in emission intensity upon the addition of L-phenylalanine however the

decrease is not significant The excitation spectrum was recorded of the emission at 545

96

nm and showed only the presence of f-f transitions and no contribution from the organic

region (Figure 214)


in D2O at pD 3 with and without the

presence of L-phenylalanine (05 M) excited at 250 nm and 379 nm Excitation

spectrum of [Tb(DTPA)]2-

in D2O at pD 3 with L-phenylalanine (05 M) at 545 nm


2522 Aqueous Phase Lanthanide Studies without Na5DTPA

Emission spectra of Eu3+

(1 mM Eu(NO3)3) were taken in D2O and H2O with the

presence of different amino acidslactate (1 M) in order to determine whether the amino

acids bind to the metal ions at pH 36 (TALSPEAK pH) The emission spectrum of the

free metal ion in solution was also measured for comparison (Figure 216)

0

100

200

300

400

500

600

700

0

5

10

15

20

25

30

220 320 420 520 620

Ab

sorp

tio

n In

ten

sity

(au

) Th

ou

san

ds

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

TbDTPA exc 379 nm

TbDTPA + Phe exc 250 nm


Excitation of TbDTPA + Phe at 545 nm

97

Figure 216 Emission spectra of Eu(NO3)3 in D2O at pD 36 with and without the

presence of amino acidslactate (1 M) excited at 395 nm at 298 K

The emission intensity increases upon the addition of amino acidslactate to Eu3+

in D2O This shows that the amino acids are interacting with the metal ion however the

emission spectra resemble that of the free aqua ion suggesting that the amino acids and

lactate are not binding to the metal ion The presence of the amino acids at such a high

concentration will reduce quenching effects from the surrounding solvent molecules

which may be one explanation for the increased emission intensity At pH 36 the

amino acids will be in their zwitterionic form (H3N+-CHR-COO

-) and so are likely to

co-ordinate with the free metal ion in the same manner as lactate however this co-

ordination appears to be very weak and they are probably in fast exchange with

surrounding water molecules

The q values of the Eu3+

ions were calculated from the luminescence lifetimes in

H2O and D2O using the original Horrocks equation (Equation 19) The results can be

seen in Table 21

0

2

4

6

8

10

12

14

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+

Eu-Lactate

Eu-Gly

Eu-Ala

Eu-Ser

98



Estimated error on lifetimes = plusmn 10 and on q plusmn 02

The number of bound solvent molecules in the inner hydration sphere of Eu3+

decreases with the addition of amino acidslactate from 9 to approximately 6 This is

consistent with possible fast exchange of water molecules with co-ordinated amino

acids and shows that an average of 3 amino acidslactate ions are co-ordinating to the

metal

2523 Aqueous Phase Lanthanide Studies with Na5DTPA

Emission spectra of Eu(NO3)3 (1 mM) with Na5DTPA (01 M) were recorded in

D2O and H2O with the presence of different amino acidslactate (1 M) at pH 36 in order

to determine whether the amino acids bind to the complexed metal (Figure 217)

Figure 217 Emission spectra of Eu-DTPA in D2O at pD 36 with and without the

presence of amino acidslactate (1 M) excited at 395 nm

0

5

10

15

20

25

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

τ in H2O (ms) τ in D2O (ms) q

Eu3+

011 165 89

Eu Lactate 016 194 60

Eu Gly 016 183 60

Eu Ala 016 187 60

Eu Ser 019 147 48

99

The emission intensity does not change upon the addition of amino acidslactate

to [Eu(DTPA)]2-

in D2O These spectra also do not change shape and there is no

observable shift resembling that of the [Eu(DTPA)]2-

species suggesting that the amino

acids and lactate are not binding to the metal complex




seen in Table 22


with amino

acidslactate Estimated error on lifetimes = plusmn 10 and on q plusmn 02

From these kinetic data it is clear that q does not change for [Eu(DTPA)]2-

upon

the addition of amino acidslactate showing that there is no significant interaction with

the Eu3+

ion and they do not bind to the metal ion of the complex This may be due to

steric factors as the DTPA5-

is octadentate and fully complexed to the metal ion leaving

room for only 1-2 solvent molecules to bind to the ion and making it difficult for any

larger species to exchange

2524 Aqueous Phase Actinide Studies with Na5DTPA

In order to determine whether amino acids interacted any more with actinides

than lanthanides the emission spectrum of [Cm(DTPA)]2-

(1 mM) was taken with the

addition of L-alanine (25 mM) at KIT-INE Karlsruhe (Figure 218)

τ in H2O τ in D2O q

Eu DTPA 063 230 23

Eu DTPA Lactate 063 216 22

Eu DTPA Gly 065 203 20

Eu DTPA Ala 065 209 21

Eu DTPA Ser 065 208 21

100


in H2O with and without L-alanine

(25 mM) at pH 3 by direct excitation at 396 nm The spectra are reported uncorrected

for differences in the incident laser power for clarity

Upon addition of L-alanine there is no change in the emission spectrum - no red

shift or change in emission intensity (quantum yield) compared to complexation of

Cm3+

to DTPA5-

(Figure 26) Moreover the luminescence lifetime is the same as

[Cm(DTPA)]2-

and there is no change in the calculated value of q indicating either no

interaction of the L-alanine with the complex or a very weak interaction such as fast

exchange of the buffer and bound solvent molecules showing that the L-alanine does

not strongly interact with Cm3+



The TALSPEAK process is known to be relatively resistant to radiation effects

both alpha and gamma radiation when compared to the PUREX and SANEX

processes33

The use of lactic acid buffer has been shown to reduce the degradation of

DTPA by radiolysis34

although the chemistry of the lactic acidlactate ion interaction

with the system is still not clear α radiolysis experiments were carried out at INL by the

Martin group initially on lactic acid and then on an L-alanine system in order to

determine the temperature-dependent rate constants of the reaction of the hydroxyl

radical (middotOH) with the buffers at pH 3 (Figure 219) It is thought that at this pH

oxidising reactions are dominant since dissolved O2 in the solution would remove most

40

45

50

55

60

65

70

75

80

570 580 590 600 610 620 630 640

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

[Cm(DTPA)]2-

[Cm(DTPA)]2- + Ala

101

of the hydrated electrons (e-(aq)) and middotH radicals caused by radiolysis leaving middotOH

radicals present in solution The rate constants were measured using Linear Accelerator

(LINAC) electron pulse radiolysis

Measurements showed that the reaction rate of the middotOH radical with L-alanine is

slower than with lactic acid suggesting that a modified version of the TALSPEAK

process using amino acids would be more resistant to radiolysis

Figure 219 Graph illustrating the rates of reaction of the middotOH radical with L-

alanine compared to lactic acid and the lactate ion 35

Further studies at the INL were carried out on the L-alanine to measure the

effect of γ-radiation on the separation of Eu3+

from Am3+

These studies were carried

out by varying the γ radiation dose (5 ndash 50 kGy) the pH (2 ndash 3) and the L-alanine

concentration (05 ndash 15 M) The extraction of Ln3+

ions was found not to be affected by

increasing the dose to both phases and the extraction of Am3+

was found to increase

only slightly as the dose was increased (Figure 220) The results show that the effect of

γ-radiation on the separation factors is negligible with increasing dose (Table 23)

32 33 34 3517

18

19

20

21

Alanine (pH 30)

Lactate ion (pH 60)

Lactic acid (pH 10)

ToC k M

-1 s

-1Error

1046 59E7 49E6

306 849E7 421E6

305 832E7 419E6

402 102E8 816E6

Arrhenius OH amp lactate at pH 30

Int ln(A) = 2353 plusmn 115

Ea = 1333 plusmn 289 kJ mol-1

R2 = 0990

ln (

kM

-1 s

-1)

103Temp (K)

102


and Am3+

in the presence of L-alanine

at 05 M pH 2 at different doses of γ-radiation36


Am3+

in the presence of L-alanine at 05 M under

TALSPEAK conditions when subjected to different doses of γ-radiationError Bookmark

not defined

Separation Factor EuAm

5 kGy 10 kGy 50 kGy 100 kGy

pH 2 5620 5519 5132 5103

pH 3 1595 1653 1589 1252


The [Eu(DTPA)]2-

systems at pH 36 were irradiated with γ radiation using a

60Co irradiator at the Dalton Cumbrian Facility to determine the effect of radiation on a

range of amino acid buffers

103


in D2O at pD 36 with and without the presence

of amino acidslactate excited at 395 nm before 5 kGy γ-irradiation



of amino acidslactate excited at 395 nm after 5 kGy γ-irradiation

The emission intensity of the irradiated samples (Figure 222) was lower than

before irradiation (Figure 221) which is likely to be due to quenching effects from

radicals produced by degradation of the solvent However the spectral profiles remain

0

50

100

150

200

250

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

0

20

40

60

80

100

120

140

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

104

the same and still resemble that of [Eu(DTPA)]2-

and t-tests showed that there was no

significant difference between the spectra of each of the buffers

The luminescence lifetimes were also measured for samples before and after

irradiation and before and after extraction into an organic phase (02 M HDEHP in

dodecane) (Table 24)


[Eu(DTPA)]2-

systems before and after irradiation at pH 36 Estimated error on

lifetimes = plusmn 10


systems before and

after irradiation at pH 36 Estimated error on lifetimes = plusmn 10 and on q = plusmn 02

τ of aqueous

phase

before

irradiation

(ms)

τ of aqueous

phase

after

irradiation

(ms)

τ of

organic

phase

before

irradiation

(ms)

τ of

organic

phase

after

irradiation

(ms)

Eu DTPA 063 066 222 262

Eu DTPA Lactate 063 063 241 251

Eu DTPA Gly 065 064 247 249

Eu DTPA Ala 065 065 211 238

Eu DTPA Ser 065 062 260 251

τ of

aqueous

phase

before

irr [H2O]

(ms)

τ of

aqueous

phase

after

irr[H2O]

(ms)

τ of

aqueous

phase

before irr

[D2O] (ms)

τ of

aqueous

phase

after irr

[D2O] (ms)

q

before

irr

q after

irr

Eu DTPA 063 066 230 227 11 10

Eu DTPA

Lactate

063 063 216 210 10 10

Eu DTPA

Gly

065 064 203 208 10 10

Eu DTPA

Ala

065 065 209 211 10 10

Eu DTPA

Ser

065 062 208 206 10 10

105

There was negligible change in luminescence lifetime before and after

irradiation for both aqueous and organic sample sets There was also no change in

hydration number q before and after irradiation of the aqueous phase (Table 25)

These data along with the consistent profiles of the emission spectra is analogous with

the radiolysis data from the INL and shows that the amino acid buffers glycine alanine

and serine are relatively resistant to -radiolysis



initially investigated by considering the interaction of the buffers glycine L-alanine L-

serine L-phenylalanine and lactate (for comparison) with Eu3+

and [Eu(DTPA)]2-

systems It was found by 1H NMR and luminescence spectroscopies that amino acids

and lactate do not form stable complexes with either the free metal ion or the metal-

DTPA complex and that the buffers may be in fast exchange with surrounding solvent

molecules Luminescence studies on L-phenylalanine showed that this amino acid does

not bind to the metal ion as there was no sensitised emission from Tb3+

ion when

excited into the phenyl chromophore of the amino acid when the two components were

in solution Emission spectra of Eu3+

and Cm3+

aqua ions and their corresponding

DTPA complexes showed no change (no peak splitting or shifting) upon the addition of

amino acidslactate

The number of water molecules in the inner hydration sphere (q) of Eu3+

was

reduced from 9 to ~6 when buffers were added to the aqua ion in solution suggesting

that the amino acids are interacting with the metal ion but are likely to be in fast

exchange with surrounding solvent molecules There was no change in q when buffers

were added to metal-DTPA complexes in solution for Eu3+

or Cm3+

Radiolysis studies were carried out on lactate and amino acid buffered

[Eu(DTPA)]2-

systems and it was found that the systems are relatively resistant to γ-

radiation when exposed to 5 kGy This is consistent with previous work conducted by

the INL showing that separation systems using L-alanine as a buffer are more resistant

to radiolysis than the original TALSPEAK process using lactate

106

1 G Muumlhlbachovaacute Rostlinnaaacute Vyacuteroba 2002 48 12 536ndash542

2 JSF Swaran and V Pachauri Int J Environ Res Public Health 2010 7 7 2745-

2788

3 M Regueiro-Figueroa and C Platas-Iglesias J Phys Chem A 2015 119 6436-

6445

4 N Mignet Q de Chermont T Randrianarivelo J Seguin C Richard M Bessodes

and D Scherman Eur Biophys J 2006 35 155-161

5 CL Davies and A-K Duhme-Klair Tetrahedron Lett 2011 52 4515-4517

6 G Moreau L Burai L Helm J Purans and AE Merbach J Phys Chem A 2003

107 758-769

7 KA Deal IA Davis S Mirzadeh SJ Kennel and MW Brechbiel J Med Chem

1999 42 15 2988ndash2992

8 S Beacutenazeth J Purans M-C Chalbot MK Nguyen-van-Duong L Nicolas K

Keller amp A Gaudemer Inorg Chem 1998 37 3667-3674

9 A Delle Site RD Baybarz J Inorg Nucl Chem 1969 31 2201

10 IA Lebedev VT Filimonov AB Shalinets GN Yakovlev Sov Radiochem

1968 10 94

11 I Bayat KFK

Berichte-1291 Karlsruhe Germany 1970

12 P Thakur JL Conca CJ Dodge AJ Francis GR Choppin Radiochim Acta

2013 101 221

13 G Tian LR Martin and LRao Inorg Chem 2015 54 1232-1239

14 S Leguay T Vercouter S Topin J Aupais D Guillaumont M Miguirditchian P

Moisy and C Le Naour Inorg Chem 2012 51 12638-12649

15 M Nazarov and D Young Noh New Generation of Europium and Terbium

Activated Phosphors 2011 247

16 K N Shinde S J Dhoble H C Swart and K Park Phosphate Phosphors for Solid

State Lighting Springer Series in Materials Science Springer 2012 174 41-59

17 K S Wong T Sun X-L Liu J Pei and W Huang Thin Solid Films 2002 417 85-

89





107

21 CF Geraldes AD Sherry WP Cacheris KT Kuan RD 3rd Brown SH

Koenig and M Spiller Magn Reson Med 1988 8 2 191-9

22 E Csajboacutek I Baacutenyai and E Bruumlcher Dalton Trans 2004 14 2152-2156

23 JJ Howland and M Calvin J Chem Phys 1950 83 239

24 J E Sansonetti and W C Martin Handbook of Basic Atomic Spectroscopic Data

httpphysicsnistgovPhysRefDataHandbookTables National Institute of Science

and Technology USA 2005

25 T Kimura and G R Choppin J Alloys Compounds 1994 213 313

26 T Kimura Y Kato H Takeishi and G R Choppin J Alloys Compounds 1998

271273 719

27 T L Griffiths Investigations of Ternary Complexes Relevant to the Nuclear Fuel

Cycle 2011 The University of Manchester PhD Thesis

28 G Tian LR Martin and L Rao Inorg Chem 2010 49 10598-10605

29 K L Nash D Brigham T C Shehee and A Martin Dalton Trans 2012 41

14547-14556

30 CJ Leggett G Liu and MP Jensen Solv Extraction and Ion Exchange 2010 28

313-334

31 A Miličević and N Raos Acta Chim Slov 2014 61 904-908

32 VV Nikonorov J Anal Chem 2010 65 4 359-365

33 D Magnusson B Christiansen R Malmbeck and JP Glatz Radiochim Acta 2009

97 9 497-502





35 LR Martin S P Mezyk and BJ Mincher J Phys Chem A 2009 113 141-145

36 Dr Leigh Martin Idaho National Laboratory unpublished results

108

3 SOLVENT EXTRACTION AND OPTIMISATION STUDIES WITH AMINO

ACID BUFFERS

As discussed in Chapter 2 the potential of using amino acids as a combined

buffer and soft donor to replace the lactate buffer and holdback reagent DTPA

(diethylenetriaminepentaacetic acid) in the TALSPEAK process (Trivalent Actinide


was investigated Initial complexation studies by 1H NMR and luminescence

spectroscopies showed that amino acids do not form stable complexes with actinide or

lanthanide ions or AnLn-DTPA complexes in aqueous solution and that like lactate

they are in fast exchange with surrounding water molecules Separation studies were

carried out by our collaborators at the Idaho National Lab (Travis Grimes Richard

Tillotson and Leigh Martin) to determine whether amino acids could be used as buffers

or as combined bufferssoft-donors to facilitate Ln3+

MA3+

separation A summary of

this work can be found below in Section 31 Their initial studies were used as the basis

for the work conducted as part of this research project (Sections 32 and 33)

31 Previous work at the INL1



L-alanine was initially chosen as a potential replacement for lactic acid as a

buffer as the two molecules differ only by the α-group (α-amino on L-alanine compared

to α-hydroxy group on lactic acid) The pKa values of the compounds are 24-26 for L-

alanine and 36-38 for lactic acid depending on the background electrolyte Studies

carried out on the L-alanine found that the separation factors were in fact reduced

compared to the traditional TALSPEAK method when L-alanine was used as a buffer at

pH 2 and pH 3 in place of lactic acid The separation factors were generally lower as the

distribution ratios for Am3+

(DAm) were significantly increased (2 orders of magnitude

higher) when L-alanine was used at pH 3 (DAm 012) and pH 2 (DAm 038-047)

compared to lactic acid at pH 3 (DAm 0009) However the studies carried out at pH 2

resembled a typical TALSPEAK curve and gave overall the best separation of

lanthanides over Am3+

as can be seen in Figure 31 Although separation occurs in the

L-alanine system at pH 3 the separation is better at pH 2 At pH 3 it can be seen that

separation is decreased for the heavier lanthanides This is due to slow phase-transfer

kinetics previously reported by Weaver and Kappelmann2 and Kolarik

3 A pH 1 system

109

does not allow separation of the earlier lanthanides from americium The distribution

ratios for lanthanides in a typical TALSPEAK system can be seen in Figure 32 for

comparison

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring

Figure 31 The effect of pH on an L-alanine-buffered TALSPEAK system


Y3+

in a TALSPEAK system 1 mM LnY3+

1 M

lactate 005 M DTPA pH 7 extracted using 05 M HDEHP in 14-DIPB4

110


The effect of the concentration of L-alanine was also considered and it was

found that the effect on the trend of separation factors across the lanthanide series was

the same as for lactate and the changes were negligible as can be seen from Figure 33

Slower extraction rates were observed for the heaviest lanthanides at lower buffer

concentrations (05 M than 10 or 15 M) for both L-alanine and lactic acid Since it was

found that there was no benefit to changing the L-alanine buffer concentration further

studies were carried out to investigate the potential of using the amino acid to carry out

the process at the lower pH of 2 as although the separation factors are lower than in

lactic acid buffered systems the values are still high enough to give sufficient

separation (see Table 31)

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring

Figure 33 The effect of buffer concentration on an L-alanine-buffered TALSPEAK

system

111

Table 31 Distribution ratios and separation factors for a number of L-alanine buffered

TALSPEAK systems as pH and buffer concentration are varied compared to a

traditional lactic acid system

Conc pH DAm Separation Factors (SF)

(M) LaAm CeAm NdAm EuAm

L-Alanine 15 2 038 plusmn 001 165 plusmn 5 61 plusmn 1 28 plusmn 1 64 plusmn 1




Lactic

Acid

10 3 0009 380 140 mdash 91


Further investigations at pH 2 into the potential of using amino acids as a

combined buffer and soft donor showed that no separation occurs when DTPA is not

present indicating that amino acids do not act as holdback reagents in their own right

Previous work by Tanner and Choppin5 showed that at low pH the glycine zwitterion

forms inner-sphere monodentate complexes with M3+

ions including Ln3+

and An3+

Aziz et al67

later showed the same is true for L-alanine with Eu3+

and Am3+

at pH 36

whereby weak monodentate complexes form Krishnan and Plane8 showed that glycine

complexes metal ions solely through the COO- group on the amino acid No co-

ordination through the amino group has been reported


Other amino acids L-arginine L-histidine and L-methionine were also

considered and further investigations were carried out (Figure 34) These three amino

acids are larger and more hydrophobic than L-alanine and are therefore less soluble at

higher concentrations (lt05 M) at pH values greater than pH 1 Again no separation

was observed when the amino acids were used without DTPA With Na5DTPA it was

found that the DAm values for Arg and Met were lower than those for L-alanine leading

to an increase in separation factor possibly due to co-ordination of the Am3+

ion with

soft donor atoms on the amino acids (Table 32) The DAm in the His system however

was similar to the Ala system suggesting that there is no coordination of the metal ion

112

with the α-amine or imidazole groups It is not known if the amino acids are co-

ordinating or chelating through soft donor atoms to the metal ion Further studies are

currently being carried out at the INL to determine stability constants and to use time-

resolved fluorescence to probe inner co-ordination sphere changes in order to

investigate the interactions of amino acids with the trivalent metal ions

Figure 34 Chemical structures of L-arginine (top) L-histidine (bottom left)

and L-methionine (bottom right)

Table 32 Distribution ratios and separation factors for a number of amino acid

buffered TALSPEAK systems

When extended further studies on these amino acids found that the kinetic

issues which affected separation of the heavier lanthanides using L-alanine at pH 3

(Figure 31) were also affecting separation with L-arginine at pH 2 as well as pH 3

Conc pH pKa DAm3+ Separation Factors (SF)


L- Arg 05 2 182 027 plusmn 001 184 plusmn 26 40 plusmn 3 27 plusmn 2 72 plusmn 4

L- His 05 2 180 040 plusmn 001 208 plusmn 8 95 plusmn 3 24 plusmn 5 83 plusmn 1

L-Met 05 2 213 017 plusmn 001 271 plusmn 18 97 plusmn 3 26 plusmn 1 60 plusmn 3

113

suggesting that longer chain amino acids may not suitable replacements for lactate

Based on these data the most promising replacement buffer is L-alanine at pH 2


Following from the initial work carried out by Grimes et al at the INL further

studies were begun for this research project The speciation of DTPA was modelled

using HySS (Hyperquad Simulation and Speciation) software using literature pKa

values (Figure 35)9 At pH 1 the dominant DTPA species present in solution are

H7DTPA2+

and H6DTPA+ which both repel MA

3+ and Ln

3+ ions and so the species are

ineffective as holdback reagents At pH 2 the dominant species are H5DTPA (65 )

H4DTPA- (24 ) and H3DTPA

2- (11 ) The species with the greatest electrostatic

attraction under these conditions is to MA3+

Ln3+

ions is H3DTPA2-

At pH 3 a much

higher proportion of this species is present (87 ) than at pH 2 making pH 2 less

favourable for effective separation However the conditions can be optimised in order

to maximise separation by changing the concentrations of extractant and holdback

reagent For industrial purposes conducting the process at a lower pH is preferable as it

is easier for process operators to control higher acid concentrations Optimisation

studies using L-alanine as a buffer at pH 2 were carried out during a placement at the

INL

114

Figure 35 DTPA speciation as a function of pH modelled using HySS sofware using

literature pKa values

321 [Na5DTPA] Dependence

The concentration of Na5DTPA used in traditional TALSPEAK systems is 005

M Initial optimisation studies were carried out using a [Na5DTPA] range of 006 M to

010 M in increments of 001 M The L-alanine concentration was 05 M

115

Figure 36 [Na5DTPA] dependence of L-alanine system (05 M) at pH 2

Experiments were carried out using traditional TALSPEAK methods at pH 2

The extractant was HDEHP (02 M) in dodecane Separations were conducted to

measure the separation of Eu3+

over Am3+

A graph of log[DTPA] vs logDEuAm can be

seen in Figure 36 The slope of the line for Am3+

is approximately -1 indicating that

the metal ions are each bound to 1 DTPA5-

molecule The R2 value is close to 1 and the

errors are small The slope of the line for Eu3+

is also approximately -1 Separation

factors for the data were between 66 and 80 and the DAm were between 026 and 042

which are still 2 orders of magnitude higher than that for a traditional TALSPEAK

system (DAm = 0009) The Na5DTPA concentration was therefore increased further in

order to bring the DAm lower to prevent as much Am3+

being partitioned into the organic

phase

y = -09383x - 15277 Rsup2 = 09854

y = -11258x + 01381 Rsup2 = 09289

-10

-05

00

05

10

15

20

-125 -12 -115 -11 -105 -1 -095

log

DEu

Am

log [Na5DTPA]

Am Extraction

Eu Extraction

116

Figure 37 Eu3+

Am3+

separation for [Na5DTPA] dependence of L-alanine system (05

M) at pH 2

Experiments were carried out as before but using Na5DTPA concentrations of

02 M 03 M 04 M and 05 M A graph of log[DTPA] vs logDEuAm was plotted

(Figure 37) At 05 M [Na5DTPA] H5DTPA began to precipitate out due to the low pH

used and so data for this concentration is unreliable and was not plotted on the graph

The data is good as the R2 values are close to 1 and the errors are small However the

slope is not exactly -1 (slope = -080 for Eu and -085 for Am) this is likely to be due to

competition and activity effects from the increased [Na5DTPA] and therefore increased

Na+ concentration Separation factors for the data were around the same (between 65

and 72) but the DAm values decreased to 008 for the 04 M Na5DTPA meaning much

less Am3+

is being partitioned into the organic phase

322 [HDEHP] Dependence

Experiments were carried out as for the [Na5DTPA] dependence but using

HDEHP extractant concentrations of 04 M 06 M 08 M and 10 M in dodecane for

each of the Na5DTPA concentrations 02 M 03 M and 04 M Graphs of log[DTPA] vs

logDEuAm were plotted (Figures 38-310)

y = -08451x - 14757 Rsup2 = 09936

y = -07958x + 03998 Rsup2 = 0998

-15

-10

-05

00

05

10

15

-11 -1 -09 -08 -07 -06 -05 -04 -03

log

DEu

Am

log [Na5DTPA]

Am Extraction Eu Extraction

117

Figure 38 Eu3+

Am3+

separation for [HDEHP] dependence of L-alanine system (05

M) at pH 2 using 02 M Na5DTPA

Figure 39 Eu3+

Am3+



y = 13522x + 02972 Rsup2 = 09283

y = 09682x + 19794 Rsup2 = 09561

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

y = 14702x + 00193 Rsup2 = 09981

y = 11892x + 17129 Rsup2 = 09713

-10

-05

00

05

10

15

20

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

118

Figure 310 Eu3+

Am3+



The R2 values for these data are close to 1 and the errors are generally small

making the data good quality The slope of each data set should be +3 indicating that

the metal ions are each bound to 3 HDEHP molecules in the organic phase1011

However the slopes are not quite +3 this is likely to be due to activity effects and

competition from the increased Na+ concentration as a result of increasing the

Na5DTPA concentration


The results of the optimisation of a TALSPEAK system using 05 M L-alanine

as a buffer are summarised in Tables 33 and 34


[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 72 plusmn 3 70 plusmn 6 43 plusmn 6 61 plusmn 9 49 plusmn 2



y = 11522x - 00047 Rsup2 = 09867

y = 12575x + 18424 Rsup2 = 09976

-10

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

119

Table 34 DAm values for L-alanine optimisation studies Error plusmn 001

[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 012 053 121 126 203

03 010 027 050 077 102

04 008 036 051 077 102

Table 33 shows the separation factors are generally similar for each condition

and there is no particular set of conditions that gives the highest value although the

better separation factors tend to be achieved at the lower extractant concentrations The

DAm values (Table 34) are best at the lowest extractant concentrations and highest

holdback concentration as would be expected The best set of conditions is 04 M

Na5DTPA and 02 M HDEHP with the best DAm achievable being 008 and best SF 71 plusmn

5 Despite optimisation the L-alanine system is still not as efficient as the traditional

lactate system as the distribution of Am3+

is one order of magnitude higher and the

separation is lower however the L-alanine system allows the separation to be carried

out at a lower pH which is beneficial for an industrial process



Several initial tests were carried out using other amino acids as buffers It had

been found previously that L-arginine at pH 2 gave poor separation of the heavier

lanthanides (Section 312) so further studies were carried out using 05 M L-methionine

and L-histidine to see how effective these amino acids could be as potential buffers

Results from initial tests using TALSEPAK conditions at varied pH values can be seen

in Table 35

120

Table 35 Separation factors and DAmEu values for traditional TALSPEAK systems

with different buffers at varying pH values

From Table 35 it can be seen that L-histidine gives good separation data at pH

3 The DAm of 007 is comparable to the optimised L-alanine system in Section 32 and

the separation factor is high at 99 comparable to the original lactate TALSPEAK

system Further investigations were subsequently carried out in order to determine if the

same kinetic issues arise with L-histidine as with L-arginine and L-alanine L-

methionine was not investigated further as the separation data at pH 2 was not very

promising and it is insoluble at 05 M at pH 3


The distribution ratios of La-Ho were determined by ICP-MS for a 05 M L-

histidine system at pH 2 and pH 3 (Figure 311)

Buffer pH DAm

DEu

SF

Lactic Acid 3 0009 0819 91

L-Methionine 1 547 6017 11

2 018 1016 57

L-Histidine 1 468 9579 20

2 053 4463 84

3 007 660 99

121


-Ho3+

and Am3+

with 05 M L-histidine buffer at

pH 2 and pH 3

The distribution ratios for the L-histidine system at pH 2 generally resemble

those on a traditional TALSPEAK curve at pH 3 with the D values decreasing towards

neodymium and then increasing with the later lanthanides However the pH 3 L-

histidine system exhibits decreasing D values with the heavier lanthanide elements

demonstrating the same kinetic problems as the L-alanine and L-arginine systems at

higher pH


Previous work carried out at the Idaho National Laboratory by Grimes showed

that amino acids do not act as holdback reagents in their own right and no separation of

Ln3+

Am3+

is achieved when they are used without Na5DTPA in solution However

investigations showed that when used alongside Na5DTPA good separation can be

attained when using 05 M L-alanine at pH 2 pH 2 is less favourable than pH 3 for

separations using DTPA as more protonated forms of the molecule are present in

solution and the holdback reagent is not able to bind as strongly to metal ions However

optimisation of the system in order to maximise the separation whilst keeping Am3+

partitioning to a minimum by changing the concentrations of holdback reagent and

extractant proved to be successful The best conditions were found to be 04 M

Na5DTPA and 02 M HDEHP giving a separation factor of 71 plusmn 5 with a DAm value of

008 Although this separation is not as good as a traditional lactate TALSPEAK

001

01

1

10

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

His pH 2

His pH 3

Am pH 2

Am pH 3

122

system the use of L-alanine as a buffer allows the process to be carried out at pH 2

which is a much more preferable pH for industry

When investigations were carried out using other amino acids at varying pH

values it was found that L-methionine was too poorly soluble at pH 3 and did not give

very good separation data at pH 2 L-arginine was found to have kinetic issues at pH 2

and 3 giving poor separation of the heavier lanthanides However L-histidine gave

good separation data at pH 3 with a SFEuAm of 99 comparable to that of the original

TALSPEAK process and a DAm of 007 comparable to the optimised alanine system

Studies of the lanthanides La-Ho using L-histidine at pH 3 however showed that the

same kinetic problems arise as for L-arginine and L-alanine as the DLn decreases for

later lanthanides indicating that L-histidine is no more promising as a buffer than the

other amino acids

123

1 TS Grimes RD Tillotson and LR Martin Solv Extraction and Ion Exchange

2014 32 378-390





3 Z Kolarik G Koch and W Kuhn J Inorg Nucl Chem 1974 36 905-909

4 KL Nash Solv Extraction and Ion Exchange 2015 33 1-55

5 S P Tanner and G R Choppin Inorg Chem 1968 7 2046-2048

6 A Aziz and S J Lyle J Inorg Nucl Chem 1971 33 3407-3408

7 A Aziz S J Lyle and J E Newbery J Inorg Nucl Chem 1971 33 1757-1764

8 K Krishnan and R Plane Inorg Chem 1967 6 55-60

9 NJ Bridges LE Roy and CL Klug Computation and Spectroscopic Investigation of

the DTPA Complexes US Department of Energy 2012

10 TS Grimes G Tian L Rao and KL Nash Inorg Chem 2012 51 6299-6307


2010 28 3 287-312

124

4 STUDIES USING L-GLUTATHIONE AS A BUFFER IN A TALSPEAK

SYSTEM

The TALSPEAK process (Trivalent Actinide Lanthanide Separation by

Phosphorus reagent Extraction from Aqueous Complexation) which is currently being

developed in the USA for separation of minor actinides (MA) from lanthanides (Ln)

from nuclear waste uses lactic acid as a buffer (pH 36) and the chelator DTPA

(diethylenetriaminepentaacetic acid) as a holdback reagent to retain Am3+

in an aqueous

phase allowing Ln3+

to be extracted by phosphate extractant HDEHP (di-

(2ethylhexyl)phosphoric acid) into an organic phase Studies have been carried out on

the potential of using amino acids as a combined buffer and soft-donor in order to

simplify the TALSPEAK process (Chapters 2 amp 3) however it was found that amino

acids do not act as holdback reagents in their own right although they have been shown

to allow the pH of the process to be lowered to pH 2 which is more favourable for an

industrial process

Although amino acids have been shown not to act as holdback reagents and are

therefore unable to replace lactic acid and DTPA5-

as a combined buffer and soft donor

based on the data obtained from the individual amino acid studies it was considered

that larger ligands with more soft donors such as short-chain peptides may be more

suitable A range of potential molecules were considered including a selection of simple

peptides including eisenin (pGlu-Gln-Ala-OH) and norophthalmic acid (γ-Glu-Ala-

Gly) (Figure 41) and B vitamins including biotin (B7) and folic acid (B9) (Figure

42)

125

Figure 41 Molecular structures of eisenin (top) and norophthalmic acid

(bottom)

Figure 42 Molecular structures of biotinvitamin B7 (top) and folic acid

vitamin B9 (bottom)

The tripeptide L-glutathione (reduced form) was chosen for further study as it

has a fairly simple structure contains several soft-donor atoms and its amino acid

constituents showed promise for buffer activity It is also relatively cheap and easy to

procure L-glutathione (GSH) consists of a chain comprising three amino acids L-

cysteinemdashL-glutamic acidmdashglycine (Figure 43)

126


Glutathione is naturally produced in all cells in the human body It is an

antioxidant with numerous functions most of which are related to the ability of its

sulphur atom to scavenge free radicals or donate electrons GSH regulates cell growth

and division by absorbing oxide radicals present in the cell which would prevent cell

growth repairs DNA by donating electrons removed from DNA strands by free radicals

aiding in DNA synthesis assists in protein synthesis by reacting (sulphur atom) with

undesirable S-S bonds to break them and allow for the correct pairing metabolises

toxins by co-ordinating with them through the S atom making them more water soluble

for excretion and recycles other antioxidants (such as vitamins C and E) by donating

electrons1 As a cysteine-containing tripeptide it is also a provider of the amino acid

cysteine in the body and is involved in amino acid transport in and out of cells

Properties of glutathione which are of particular interest to MA3+

Ln3+

separation

studies are its ability to conjugate to heavy metals (to allow them to be removed from

the body like DTPA23

and its resistance to radiation (due to its ability to scavenge free

radicals) which decreases radiation damage in the body45

but also would be beneficial

for spent nuclear fuel (SNF) reprocessing where free radicals and high levels of

radiation are present

As is the case for lactate6 and amino acid

7 complexes of lanthanides stability

constants of Ln-GSH complexes increase across the lanthanide series from La-Lu as the

Lewis acidity of the metal ions increases Log β values range from 556 for La3+

to 751

for Ho3+

with GSH indicating slightly higher stability of Ln-GSH complexes than of

lactate and amino acid complexes of Ln3+

with log β = 633 for Ln(lactate)3 formation

and values ranging from 582-665 for L-alanine with Ln3+

when Ln = La-Sm (Section

242) Garg et al also reported that the stability of Ln-GSH complexes was found to

decrease as ionic strength increases and that the optimum stability of the complexes was

in solutions within the pH range of 340-348 (77 complex formation)8

127

Solvent extraction experiments were initially performed in order to investigate

the separation ability of GSH with Am3+

and Eu3+

and conditions were then optimised

in order to achieve maximum separation Interaction of the buffer with various



susceptibility of the buffer to radiolysis and ICP-MS



4111 [GSH] Dependence without Na5DTPA at pH 4

L-glutathione has pKa values of 212 (COOH) 359 (COOH) 875 (NH2) and

965 (SH)9 and so with two pKa values below 4 and optimum stability at pH 34 initial

studies were carried out at pH 4 as it would be expected that the glutathione would

complex to metal ions most effectively around this pH and be more likely to act as a

holdback reagent Although pH 4 is a higher pH than that used currently in the

TALSPEAK process and therefore less desirable if proven to improve the process it

may still have potential if satisfactory separation is achieved

Initial studies using L-glutathione as a buffer without the presence of Na5DTPA

in the system showed that as with amino acids GSH is ineffective as a holdback

reagent on its own as there was no separation observed between Eu3+

and Am3+

Over a

GSH concentration range of 01 M to 05 M the separation factors ranged from 038-

585 plusmn 108 Glutathione is insoluble at concentrations above 05 M at pH 4 at room

temperature


Further experiments were then carried out using GSH as a buffer in the presence

of Na5DTPA in order to see if there was any improvement in the separation with this

buffer over the traditional lactic acid buffer The experiments used 005 M Na5DTPA

and 01-05 M GSH over a pH range of 2-4 under TALSPEAK conditions (02 M

HDEHP in n-dodecane)

128

Figure 44 Eu3+

Am3+

distribution for [GSH] dependence with 005 M Na5DTPA at pH

2 extracted using 02 M HDEHP in dodecane Results were averaged from 3 repeat

tests

Figure 45 Eu3+

Am3+



tests

Plots of log[GSH] vs logDEuAm for systems at pH 2 and 3 are displayed in

Figures 44 and 45 The graphs show that increasing the concentration of GSH does not

affect the separation of Eu3+

over Am3+

since the distribution ratios for each remain

-02

0

02

04

06

08

1

12

14

16

18

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

-1

-08

-06

-04

-02

0

02

04

06

08

1

12

14

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

129

relatively constant At pH 2 the average DAm is 103 and DEu is 3013 giving an

average separation factor of 29 plusmn 8 At pH 3 the extraction of both metals is lower with

DAm averaging at 018 and DEu at 1423 giving an average separation of 79 plusmn 13 Both

data sets for pH2 and pH 3 show a slope of almost zero suggesting that the metal ions

are not bound to any GSH molecules which would be consistent with the L-glutathione

just acting as a buffer These separation factors are lower than for the original

TALSPEAK buffered system using lactate (SF = 91 at pH 36) However at pH 4 the

slopes change on the graph and a difference in separation can be observed as the molar

concentration of GSH is increased

Figure 46 Eu3+

Am3+


4 Results were averaged from 3 repeat tests

At pH 4 as the concentration of L-glutathione is increased the separation factor

increases (Figure 46) The value DEu initially increases as the GSH concentration is

increased from 01-02 M but then remains constant at ~6 However DAm values

decrease linearly as the buffer concentration is increased from 01-05 M giving rise to

increased partitioning and separation values The results from the extraction

experiments at pH 4 are given in Table 41

-15

-10

-05

00

05

10

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

130

Table 41 Eu3+

Am3+

distribution and separation for [GSH] dependence with 005 M

Na5DTPA at pH 4

[GSH] (M) DAm DEu SF

01 073 plusmn 027 100 plusmn 041 14 plusmn 13





The results show that the L-glutathione is interacting with the DTPA in some

way at pH 4 to allow the separation to increase as a function of GSH concentration only

in the presence of Na5DTPA up to a SF of 104 at 05 M GSH concentration

comparable to separation achieved in the original lactate buffered TALSPEAK process

Figure 47 GSH speciation as a function of pH modelled using HySS software using

literature pKa values of 212 (COOH) 359 (COOH) 875 (NH2) and 965 (SH)9

131


The speciation of GSH at pH 4 was modelled using HySS (Hyperquad Simulation and

Speciation) software using literature pKa values (Figure 47) At pH 4 the dominant

GSH species is the H2GSH- species (Figure 48) with both carboxylic acids

deprotonated This suggests that deprotonation of the second COOH group allows the

ligand to interact through the COO- to the metal complex Indeed several studies by

Faulkner et al have shown that molecules containing carboxylate functionalities

readily bind with 7-coordinate lanthanide(III) polyaminocarboxylate complexes in a

bidentate manner here DO3A (DO3A = [4710-tris-carboxymethyl-14710-tetraaza-

cyclododec-1-yl]-acetic acid) (Figure 49) and a similar binding interaction with the

related DTPA actinide(III)lanthanide(III) may be anticipated

Figure 49 A ternary Nd DO3A-pyrazine amine carboxylate complex reported by

Faulkner at al (left) and anticipated bidentate chelation of GSH with Am-DTPA at pH

4 (right)10

132


The highest concentration of buffer (05 M) gave the highest separation factors

in the [GSH] dependence study at pH 4 so this concentration was chosen for the next

study on [Na5DTPA] dependence (Figure 410) Relatively high concentrations of

Na5DTPA were chosen (005-06 M) to make the results comparable to those obtained

in the optimisation of the L-alanine system (Section 32) The graphs plotted for the

[Na5DTPA] dependence were not plotted as log plots as it is not known how the

Na5DTPA and GSH interact and what competition effects may be present so the direct

correlation between the complexant concentration and D values have been plotted to

make interpretation more simple

Figure 410 Eu3+

and Am3+

distribution for [Na5DTPA] dependence with 05 M GSH

buffer at pH 4 curves fitted as polynominal order 2 for both Am3+

and Eu3+

Results

were averaged from 3 repeat tests

y = 19018x2 - 23123x + 72258 Rsup2 = 09937

y = 0442x2 - 03543x + 00659 Rsup2 = 0781

00

00

01

01

02

-20

-10

00

10

20

30

40

50

60

70

-01 26E-15 01 02 03 04 05 06 D

Am

DEu

[Na5DTPA] (M)

Eu extraction

Am extraction

133

Table 42 Eu3+

Am3+

distribution and separation for [Na5DTPA] dependence with 05

M GSH buffer at pH 4

[Na5DTPA] (M) DAm DEu SF

005 00650 plusmn ˂0001 624 plusmn 076 96 plusmn 11







These data show that as the concentration of Na5DTPA is increased the

separation factor increases dramatically up to 03 M Na5DTPA with a maximum of

1037 85 (Table 42) After this peak there is a rapid decrease in separation as the

concentration of Na5DTPA is increased further up to 06 M The DAm decreases at a

steady rate as [Na5DTPA] is increased from 005 M to 04 M after which the DAm

increases slightly and remains fairly constant The DEu decreases at a slower rate

between 005 M and 02 M complexant decreasing more rapidly from 02 M to 06 M

The SF significantly decreases as the concentration of Na5DTPA is increased from 04

to 05 M Although it is unclear why this is without detailed structural analysis the

stoichiometry of DTPAGSH becomes 11 at 05 M which may alter the interaction

between the two constituents The separation factors achieved here are extremely high

(a factor of 10 higher than the current TALSPEAK system and the optimised alanine

system (Chapter 3)) whilst still maintaining low extraction of Am3+


The extractant concentration dependence was measured for the systems

containing 05 M buffer and 03 M and 04 M Na5DTPA These Na5DTPA

concentrations were chosen for comparison as the 03 M was found to give the highest

separation factor and 04 M seemed to be the point where the separation began to

decrease The graphs plotted for the [HDEHP] dependence have also been plotted by

direct correlation between the extractant concentration and D values

134

Figure 411 Eu3+

and Am3+

distribution for [HDEHP] dependence with 03 M

Na5DTPA and 05 M GSH buffer at pH 4 curve for Eu3+

fitted as polynominal order 2

linear correlation for Am3+


Table 43 Eu3+

Am3+

distribution and separation for [HDEHP] dependence with 03 M

Na5DTPA and 05 M GSH buffer at pH 4

[HDEHP] (M) DAm DEu SF






At 03 M Na5DTPA the separation factor increases as the extractant

concentration is increased from 02 to 04 M after which the SF begins to decrease

again (Figure 411) The DAm increases slightly as the HDEHP concentration is

increased but the DEu increases and then decreases like the SF The separation factors

for the lower concentrations of extractant are very high with the optimum separation at

04 M giving a SF of 1238 (Table 43)

y = -30649x2 + 3243x + 15029 Rsup2 = 09467

y = 00013x + 00015 Rsup2 = 08028

0000

0002

0004

0006

0008

0010

0012

0014

00

05

10

15

20

25

30

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

135

Figure 412 Eu3+

and Am3+


Na5DTPA and 05 M GSH buffer at pH 4 linear correlation for both Am3+

and Eu3+


Table 44 Eu3+

Am3+









At 04 M Na5DTPA the separation factor decreases rapidly as the extractant

concentration is increased The DAm increases by a factor of 1000 but the DEu only

decreases slightly making the SF decrease significantly (Figure 412 and Table 44)

This would be consistent with the complexant and buffer interacting at higher

Na5DTPA concentrations as the stoichiometry nears 11 possibly forming an adduct

which no longer successfully holds back Am3+

Further structural studies are needed on

these systems in order to determine the complexation mechanisms in the solution under

these conditions

y = -01882x + 08847 Rsup2 = 08326

y = 17968x - 04007 Rsup2 = 09946

-0500

0000

0500

1000

1500

2000

00

01

02

03

04

05

06

07

08

09

10

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

136


Further studies on the glutathione systems were carried out on lanthanide

systems in order to gain some insight into the co-ordination of the buffer with the ions

with and without Na5DTPA present Control measurements were taken of Eu(NO3)3 in

water with no other reagents Eu(NO3)3 with Na5DTPA with no GSH and Eu(NO3)3

with GSH without Na5DTPA for comparison purposes (Figure 413) All luminescence

spectra were recorded and averaged from 5 repeat measurements

Figure 413 Corrected emission spectra of Eu(NO3)3 (1 mM) Eu(NO3)3 with GSH (05

M) and Eu(NO3)3 with Na5DTPA (005 M) in H2O following excitation at 397 nm

A first set of experiments was then carried out to mimic the separation and

solvent extraction studies performed at the INL (Section 41) At the same concentration

of Eu(NO3)3 the J=2 band of Eu3+

increases in intensity upon the addition of GSH

indicating a change in symmetrycrystal field and a weak but detectable interaction with

GSH (the J=1 and J=4 bands are the same intensity with and without GSH) Upon the

addition of Na5DTPA to the system the crystal field changes and the J=4 band shifts

position slightly indicating that a different species is forming which is consistent with

the formation of [EuDTPA]2-

0

1

2

3

4

5

6

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+ in H2O

Eu with GSH

Eu with DTPA

137

421 [GSH] and pH Dependence without DTPA at pH 4



(1 mM Eu(NO3)3) in H2O and D2O were measured at

pHpD 4 as the concentration of [GSH] was varied from 01 M to 05 M The spectra

can be seen in Figures 414 and 415

Figure 414 Emission spectra of Eu(NO3)3 in H2O at pH 4 over a GSH concentration

range of 01 ndash 05 M following excitation at 397 nm

The spectra show an increase in emission intensity of the J=2 band as the GSH

concentration is increased from 01-02 M followed by a decrease at 03 M and a

further increase at 04 and 05 M whereas the opposite trend is observed with the J=4

peak The J=1J=2 peak ratios were determined and a t-test was carried out on them to

determine whether they were significantly different and hence whether the co-ordination

mode of the GSH to the Eu3+

changed as the buffer concentration was increased The

J=1J=2 values ranged from 0364-0718 and were found to be significantly different

The spectra are similar to that recorded for the free ion in solution but the J=1J=2

ratios vary slightly and there are some differences in the fine structure of the emission

bands This indicates that GSH is interacting with Eu3+

under these conditions albeit

weakly and the surrounding water molecules are in fast exchange with the buffer

molecules The solution dynamics were investigated further and the spectra were

recorded in D2O in order to minimise quenching caused by fast exchange of O-H

oscillators and to determine the inner sphere hydration number of Eu3+

in each case (q)

00

01

02

03

04

05

06

07

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

138

Figure 415 Emission spectra of Eu(NO3)3 in D2O at pH 4 over a GSH concentration


In D2O it can be seen that the emission intensity increases as the GSH

concentration is increased from 01-03 M followed by a decrease at 04 M and a slight

increase at 05 M This time the J=1J=2 values ranged from 0324-0748 but were

found not to be significantly different suggesting that the co-ordination mode of the

GSH to the metal ion is not changing as the concentration is increased which would be

expected as the buffer is not forming a stable complex with the ion and is in exchange

with surrounding solvent molecules

The number of water molecules bound to the Eu3+

ion (q) was calculated for

each of the samples using the Horrocks equations (Equations 19 and 110) The results

can be found in Table 45 There is a large range in q between different concentrations

with no clear pattern to the lifetimes or number of bound water molecules other than

generally q tends to increase from around 1 to 5 at the highest concentrations of GSH

This could be explained by the increasing ionic strength decreasing the stability of any

Eu-GSH complex and the solvent molecules are also in fast exchange with the buffer

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

139


with GSH at pHD 4

Error on lifetimes plusmn 10

[GSH]

(M)

τ D2O (μs) τ H2O (μs) q plusmn 02

01 1487 428 17

02 785 353 16

03 829 440 11

04 1545 161 58

05 1016 168 52


Extractions were carried out on the Eu3+

samples containing GSH using 02 M

HDEHP in dodecane for the organic phase The emission spectra of both the aqueous

and organic phases post-extraction can be seen in Figure 416


extraction at

pH 4 using a GSH concentration range of 01 ndash 05 M following excitation at 397 nm

The Eu-HDEHP complex formed in the organic phase has different symmetry to

Eu3+

complexes in the aqueous phase as can be seen by the different profile of the

emission spectra of the organic phases The spectra show good extraction of the Eu3+

into the organic phase for all concentrations of GSH with little or no metal ion left in the

aqueous phase The J=1J=2 values ranged from 0794-1214 for the organic phase and

were found not to be significantly different as expected as the buffer is unlikely to

00

01

01

02

02

03

03

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH Aq 02 M GSH Aq 03 M GSH Aq 04 M GSH Aq 05 M GSH Aq 01 M GSH Org 02 M GSH Org 03 M GSH Org 04 M GSH Org 05 M GSH Org

140

affect the co-ordination of metal ion in the organic phase as the Eu3+

ion is extracted as

the HDEHP complex seen by the different emission profile in the organic phase

spectrum11

422 [GSH] and pH Dependence with DTPA



(1 mM Eu(NO3)3) in H2O and D2O with 005 M

Na5DTPA were measured over a pHpD range of 2-4 as the concentration of [GSH] was

varied from 01 M to 05 M The D2O spectra can be seen in Figures 417 to 419 The

H2O spectra closely resemble those recorded in D2O but with lower relative emission

intensites as expected (Appendix 1)


in D2O at pD 2 with 005 M Na5DTPA over a

GSH concentration range of 01 ndash 05 M following excitation at 397 nm

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

141







It can be seen that in all samples a Eu-DTPA complex has formed The spectra

are all almost identical for each pD and for each buffer concentration with the emission

intensity being slightly higher for pD 3 and 4 with the same concentration of Eu3+

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

142

Table 46 J=1J=2 peak ratios and t-test results for Eu-DTPA at pD 2-4 over a GSH

concentration range of 01-05 M following excitation at 397 nm

J=1J=2

[GSH] (M)

01 02 03 04 05 st dev t-test

pD 2 0335 0399 0379 0375 0361 0024 No sig diff

pD 3 0440 0433 0451 0439 0419 0012 No sig diff

pD 4 0438 0467 0413 0469 0454 0023 No sig diff

st dev 0060 0034 0036 0048 0047

t-test Sig diff Sig diff Sig diff Sig diff Sig diff

The J=1J=2 peak height ratios were recorded for each emission spectrum and t-

tests were carried out on the peak ratios using the t-test data analysis tool in Microsoft

Excel accounting for the standard deviations between the ratios (Table 46) For each

pH as the concentration of GSH is increased the range in the ratios remains small and

there is no significant difference between the values suggesting that there is no change

in the co-ordination mode of the buffer to the metal ion as the concentration of GSH is

increased However a significant difference was observed between the data sets upon

changing pH as the J=1J=2 ratio increases from pD 2 to pD 4 indicating that the co-

ordination mode of glutathione is different at different pH values This is consistent

with the pKa values of GSH as at pH 2 both of the carboxylate groups will be

protonated with the dominant species present in solution shifting from 5050

H3GSHH2GSH to 5050 H4GSHH3GSH (Figure 47)

The luminescence lifetimes of each sample were recorded in H2O and D2O in

order to determine the q value of the complexes using the modified Horrocks equation

(Equation 110) These results are summarised in Table 47

143

Table 47 Luminescence lifetimes and q values for Eu-DTPA at pH 2-4 over a GSH


[GSH] (M) τ D2O (μs) τ H2O (μs) q plusmn 02

pH 2 01 1699 plusmn 7 607 plusmn 9 10

pH 2 02 1692 plusmn 10 619 plusmn 10 09

pH 2 03 1686 plusmn 9 629 plusmn 9 09

pH 2 04 1636 plusmn 12 607 plusmn 13 09

pH 2 05 1596 plusmn 11 629 plusmn 13 09

pH 3 01 1755 plusmn 14 626 plusmn 7 09

pH 3 02 1737 plusmn 13 626 plusmn 15 09

pH 3 03 1723 plusmn 5 626 plusmn 13 09

pH 3 04 1720 plusmn 14 635 plusmn 17 09

pH 3 05 1677 plusmn 9 641 plusmn 14 09

pH 4 01 1778 plusmn 14 593 plusmn 16 10

pH 4 02 1747 plusmn 13 640 plusmn 15 09

pH 4 03 1679 plusmn 15 669 plusmn 18 08

pH 4 04 1689 plusmn 14 623 plusmn 15 09

pH 4 05 1679 plusmn 13 652 plusmn 19 08

All of the complexes have approximately 1 water molecule in the inner

hydration sphere This is consistent with the formation of a [Eu(DTPA)]2-

complex The

values are only slightly less than 1 (compared to [Eu(DTPA)]2-

itself where q = 11)

and in most cases is not significantly different This indicates that any interaction of

GSH with the Eu3+

centre is very weak and that the buffer may be in fast exchange with

the bound water molecule


Extractions were carried out on the samples using 02 M HDEHP in dodecane

for the organic phase in the absence of DTPA The emission spectra of both the aqueous

and organic phases post-extraction can be seen in Figures 420 and 421

144


extraction at pH 2-4 over a

GSH concentration range of 01-05 M following excitation at 397 nm




The extraction data show that the best Eu3+

extraction occurs at pH 3 under these

conditions although as seen from the separation data obtained at INL (Section 41) this

is not the best pH for separation of metal ions The J=1J=2 peak height ratios were

recorded for each emission spectrum and t-tests were carried out on the peak ratios

using the t-test data analysis tool in Microsoft Excel accounting for the standard

deviations between the ratios The J=1J=2 peak ratios for the aqueous phases show no

significant difference within the pH 4 data as the GSH concentration is increased and

00

05

10

15

20

25

30

35

40

45

50

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Aq

03 M GSH pH 4 Aq

05 M GSH pH 4 Aq

05 M GSH pH 3 Aq

05 M GSH pH 2 Aq

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Org

03 M GSH pH 4 Org

05 M GSH pH 4 Org

05 M GSH pH 3 Org

05 M GSH pH 2 Org

145

the standard deviation is small (Table 48) however a significant difference is observed

between each of the pH values for the same buffer concentration 05 M which is again

consistent with the co-ordination mode of glutathione changing with pH Interestingly

under these experimental conditions the extraction of Eu3+

as the HDEHPDEHP

organic soluble complexes is not very efficient since the emission intensities are

unusually low This suggests that in the absence of competing Am3+

ions GSH is

interacting relatively strongly with the Eu3+

ion in aqueous solution

Table 48 J=1J=2 peak ratios and t-test results for Eu-DTPA at pH 2-4 as [GSH] is

varied

J=1J=2

[GSH] (M)

01 03 05 st dev t-test

pD 4 0202 0276 0247 0037 No sig diff

pD 3 - - 0100 - -

pD 2 - - 0500 - -

st dev - - 0202

t-test - - Sig diff



The [Na5DTPA] dependence study carried out at the INL was also repeated in

order to gain luminescence data for the experiment The conditions used were pH 4 05

M GSH and [Na5DTPA] concentrations ranging from 005 ndash 06 M The emission

spectra can be seen in Figure 422

146

Figure 422 Emission spectra of Eu(NO3)3 in D2O at pD 4 with 05 M GSH over a

Na5DTPA concentration range of 005 ndash 06 M following excitation at 397 nm

The emission intensity of the complex decreases as the concentration of

Na5DTPA is increased from 005 M to 06 M This is likely to be due to the introduction

of more O-H oscillators and therefore increased quenching as the Na5DTPA stock

solution is aqueous and there is no deuterated alternative available The emission

spectra in water do not show this decrease in intensity (Figure 423)

Figure 423 Emission spectra of Eu(NO3)3 in H2O at pH 4 with 05 M GSH over a


0

5

10

15

20

25

30

35

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

0

2

4

6

8

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

147

Table 49 J=1J=2 peak ratios and t-test results for Eu-DTPA with 05 M GSH in

D2OH2O at pDpH 4 over a Na5DTPA concentration range of 005-06 M

J=1J=2

[Na5DTPA] (M)

005 01 02 03 04 05 06 stdev t-test

D2O 0437 0441 0431 0437 0428 0425 0403 0013

No sig

diff

H2O 0450 0440 0437 0449 0422 0424 0428 0011

No sig

diff



Excel accounting for the standard deviations between the ratios The J=1J=2 peak

ratios show no significant difference for either the D2O or H2O samples as the

Na5DTPA concentration is increased (Table 49) suggesting that the co-ordination

mode of the DTPA does not change as the concentration is increased The luminescence

lifetimes of the samples show a decrease across the D2O samples as the concentration of

Na5DTPA increases This is consistent with the decreased emission intensity due to

greater quenching of the samples as more water is introduced However there is a slight

increase across the H2O samples as the holdback concentration increased as quenching

is reduced in these samples due to the chelating effect of the DTPA molecules therefore

the results obtained in water for this study are likely to be most accurate The lifetimes

and q values are tabulated in Table 410 Although the q values are likely to be

unreliable especially for the highest Na5DTPA concentrations it can be seen that there

is still approximately 1 H2O molecule in the inner hydration sphere of the complexes

consistent with [Eu(DTPA)]2-

formation again implying very little or weak binding

with GSH

148

Table 410 Luminescence lifetimes and q values for Eu-DTPA with 05 M GSH at pH

4 over a Na5DTPA concentration range of 005-06 M following excitation at 397 nm

[Na5DTPA]

(M)


005 1679 plusmn 3 652 plusmn 2 08

01 1549 plusmn 4 659 plusmn 2 10

02 1348 plusmn 4 666 plusmn 3 09

03 1179 plusmn 4 665 plusmn 3 08

04 1076 plusmn 4 674 plusmn 4 07

05 978 plusmn 4 698 plusmn 4 05

06 916 plusmn 5 714 plusmn 5 03



for the organic phase The emission spectra of both the aqueous and organic phases

post-extraction can be seen in Figure 424


extraction with

05 M GSH at pH 4 over a Na5DTPA concentration range of 005-06 M following


0

1

2

3

4

5

6

7

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

149

As expected the extraction data show that the best Eu3+

extraction occurs with

01 M Na5DTPA the lowest concentration of holdback reagent and that very little

extraction occurs at 03 M and 05 M Na5DTPA under these conditions The J=1J=2

peak ratios for the aqueous phases show no significant difference as the Na5DTPA

concentration is increased (Table 411) Unfortunately here the extraction is too weak

and the emission intensity too low to obtain reliable J=1J=2 peak ratios for the organic

phase


in the aqueous phase with 05

M GSH at pH 4 as [Na5DTPA] is varied after extraction with 02 M HDEHP

Na5DTPA (M) 01 03 05 st dev t-test

J=1J=2 0552 0578 0502 0039 No sig

diff


An HDEHP concentration dependence study was carried out under the same

conditions as the study at INL 05 M GSH 03 M Na5DTPA pH 4 and an extractant

concentration range of 04-10 M HDEHP in dodecane Equilibration time was for 30

minutes The emission spectra of the phases after extraction can be seen in Figures 425

and 426

150


extraction with 05 M GSH

and 03 M Na5DTPA at pH 4 over an HDEHP concentration range of 02-10 M


The J=1J=2 peak ratios for the aqueous phases show no significant difference as

the HDEHP concentration is increased (Table 412) as expected since the co-ordination

mode of the aqueous phase should be unaffected by the organic phase Unfortunately

again the extraction is too weak and the emission intensity too low to obtain reliable

J=1J=2 peak ratios for the organic phase



M GSH and 03 M Na5DTPA at pH 4 as [HDEHP] is varied after extraction

HDEHP (M) 04 06 08 10 st dev t-test

J=1J=2 0472 0499 0455 0510 0025 No sig

diff

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Aq

06 M HDEHP Aq

08 M HDEHP Aq

10 M HDEHP Aq

151





The lowest Eu3+

extraction is with 04 M HDEHP with better extraction at

higher HDEHP concentrations Although better extraction is obtained at higher

concentrations Am3+

is also extracted to a higher extent decreasing the separation

factor (Section 413)



In order to determine how resistant the glutathione buffered system is to

radiolysis a selection of aqueous samples at pHpD 4 containing 05 M GSH and a

Na5DTPA concentration range of 005-06 M were irradiated at the Dalton Cumbrian

Facility using a 60

Co irradiator The samples were exposed to 7 kGy γ-radiation and

analysed by luminescence spectroscopy The emission spectra of the samples can be

seen in Figure 427

00

00

00

01

01

01

01

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Org

06 M HDEHP Org

08 M HDEHP Org

10 M HDEHP Org

152


Na5DTPA concentration range of 005 ndash 06 M after irradiation with 7 kGy γ-radiation


The spectra of the samples show a lower emission intensity after irradiation

(Figure 427) than beforehand (Figure 423) but the profile remains the same indicating

that the radiation has little or no degrading effect on the complex in the aqueous phase

The decreased intensity is likely to be due to increased quenching effects caused by

residual radicals present as a result of irradiating the solvent The J=1J=2 ratios and co-

ordination mode remained unchanged (Table 413) as did the luminescence lifetimes of

the samples and the q values (Table 414)

00

01

01

02

02

03

03

04

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

153


D2OH2O at pDpH 4 over a Na5DTPA concentration range of 01-06 M after

irradiation with 7 kGy γ-radiation

[Na5DTPA] (M)

01 02 03 04 05 06 st

dev

t-test

J=1J=2 0477 0481 0452 0401 0407 0411 0036

No sig

diff

Table 414 Luminescence lifetimes and q values for Eu-DTPA with 05 M

GSH at pH 4 over a Na5DTPA concentration range of 01-06 M after irradiation with 7

kGy γ-radiation

[Na5DTPA] (M) τ H2O (μs) τ D2O (μs) q plusmn 02

01 648 plusmn 4 1895 plusmn 12 10

02 661 plusmn 6 1678 plusmn 10 09

03 670 plusmn 6 1536 plusmn 11 08

04 679 plusmn 5 1462 plusmn 9 07

05 701 plusmn 7 1328 plusmn 10 05

06 696 plusmn 6 1211 plusmn 8 03


Extractions were then carried out on a selection of the irradiated samples using

02 M HDEHP in dodecane with Eu3+

The resultant emission spectra of both the

aqueous and organic phases post-extraction can be seen in Figure 428

154


extraction from

irradiated aqueous phase at pH 4 containing 05 M GSH over a Na5DTPA concentration

range of 01-06 M




extraction occurs at 03 M and 05 M Na5DTPA under these conditions With the

exception of the 01 M Na5DTPA sample for which the extraction decreases after

irradiation the emission intensity remains relatively constant for each of the phases of

the samples after irradiation The J=1J=2 ratios and co-ordination mode for the aqueous

phase remained unchanged (Table 415) Again the extraction is too weak and the

emission intensity too low to obtain reliable J=1J=2 peak ratios for the organic phase



M GSH and at pH 4 as [Na5DTPA] is varied after extraction with 02 M HDEHP in

dodecane from an aqueous phase irradiated at 7 kGy γ ndashradiation


J=1J=2 0505 0563 0551 0031 No sig diff


As well as obtaining primary extraction data for GSH with Eu3+

under a variety

of conditions it is also important to consider the behaviour and extraction of other Ln3+

ions with the buffer in order to achieve effective lanthanide-actinide separation

0

1

2

3

4

5

6

7

8

9

10

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Hu

nd

red

s

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

155

Dysprosium(III) was chosen for a preliminary study as it is later in the lanthanide series

representing the heavier metal ions and how they may behave under such conditions

Also like Eu3+

it is emissive in the visible region of the electromagnetic spectrum and

so may be easily analysed by luminescence spectroscopy

441 Dy3+


Initial data were obtained for Dy3+

and emission spectra were recorded for the

free ion from Dy(NO3)3 Dy-DTPA (005 M Na5DTPA) and Dy(NO3)3 with GSH (05

M) all in aqueous solution (Figure 429) A concentration of 005 M Na5DTPA was

chosen for the dysprosium experiments as the emission intensity of Dy3+

is relatively

weak and this technique is not sensitive enough to observe any extraction of the metal

from high Na5DTPA concentrations

Figure 429 Emission spectra of Dy(NO3)3 (10 mM) Dy-DTPA (10 mM Dy(NO3)3

005 M Na5DTPA) and Dy(NO3)3 (10 mM) with GSH (05 M) in H2O following

excitation at 352 nm Note that the tail of ligand emission can be seen in the Dy DTPA

and Dy GSH solutions at shorter wavelengths

The spectra show that the emission intensity of the 7F92 rarr

6H152 and

7F92 rarr

6H132 transitions is slightly higher when GSH buffer is present in solution than for the

free ion alone and the intensity is much greater when Na5DTPA is present in the

solution showing formation of a Dy-DTPA complex Interestingly evidence for

binding of GSH and DTPA with Dy3+

is further manifested in the emission spectra by

the presence of residual ligand emission at higher energy These samples were then

00

02

04

06

08

10

12

14

16

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O

Dy DTPA

Dy GSH

7F92 rarr

6H152

7F92 rarr

6H132

156

extracted into an organic phase of 10 M HDEHP in dodecane (Figure 430) as 02 M

extractant was found to be too low to observe any Dy3+

extraction due to the overall

weak emission of the ion relative to Eu3+

Figure 430 Emission spectra of aqueous and organic phases of Dy(NO3)3 Dy-DTPA

and Dy(NO3)3 with GSH after extraction with 10 M HDEHP following excitation at

352 nm

The spectra show that without Na5DTPA present the Dy3+

is extracted into the

organic phase but for the Dy-DTPA complex little or no metal extraction is observed in

the absence of competitive binding with Am3+

This may indicate that the metal is not

being extracted into the organic phase and that the heavier lanthanides may suffer the

same kinetic issues present for amino acid buffers at higher pH (Section 332) or that

this technique is not sensitive enough to obtain good extraction data for less emissive

lanthanides


To attempt to determine whether kinetic issues arise for heavier lanthanides with

GSH buffer at higher pH values a pH study was carried out on Dy-DTPA systems

containing 005 M Na5DTPA and 05 M GSH over a pH range of 2-4 One sample

containing 03 M Na5DTPA was also measured analogous to the europium data sets

The extraction data can be seen in Figure 431

00

02

04

06

08

10

12

14

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O Aq

Dy DTPA Aq

Dy GSH Aq

Dy H2O Org

Dy DTPA Org

Dy GSH Org

157


and Dy(NO3)3 with GSH after extraction with 10 M HDEHP following 352 nm

excitation

The extraction is lowest for the sample with the highest Na5DTPA

concentration as would be expected As the pH increases the extraction of Dy3+

decreases suggesting that the same kinetic issues may also be present in for the GSH

system Further investigation using a more sensitive technique such as ICP-MS is

necessary to confirm this (Section 46)


Systems at pH 4

The Dy3+

luminescence work was extended to solutions of a mixture of 4

luminescent lanthanide ions (Sm3+

Eu3+

Tb3+

and Dy3+

) to be able to probe the relative

extraction of different lanthanides from a mixture relevant to a real TALSPEAK type

process The spectra are colour coded to each ionrsquos luminescent colour under UV light

irradiation


Initial data were obtained for each lanthanide ion and emission spectra were

recorded for Ln(NO3)3 Ln-DTPA (005 M Na5DTPA) and Ln(NO3)3 with GSH (05

M) all in aqueous solution (Figures 432-434) analogous to the Dy3+

data

00

01

02

03

04

05

06

07

08

09

10

550 560 570 580 590

Emis

sio

n In

ten

sity

(au

) x 1

00

00

Wavelength (nm)

pH 2 Aq

pH 3 Aq

pH 4 Aq

pH 4 (03 M DTPA) Aq

pH 2 Org

pH 3 Org

pH 4 Org

pH 4 (03 M DTPA) Org

158


10 mM Dy3+

) in H2O

at pH 4 following direct excitation (405 nm for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10 mM Dy3+

) with

GSH (05 M) at pH 4 in H2O following direct excitation (405 nm for Sm3+

397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

0

5

10

15

20

25

30

35

40

45

50

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

0

2

4

6

8

10

12

14

16

18

20

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

159


10 mM Dy3+

005 M

Na5DTPA) in H2O at pH 4 following direct excitation (405 nm for Sm3+

397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

For all of the metal ions the emission intensity is greater in the sample with

GSH than for the free ions in solution due to reduced quenching by the presence of the

buffer The profiles of all of the spectra remain the same showing that although the

glutathione may be in exchange with surrounding water molecules a stable complex

between the buffer and metal ions is not being formed The emission intensity is much

greater for each of the metal ions with Na5DTPA due to the formation of a Ln-DTPA

complex in each case and the peak splitting observed for the Eu3+

complex can also be

seen for the Tb3+

complex as the emission spectra of these ions are more sensitive to

their co-ordination environment than Sm3+

or Dy3+


Sample Lifetime (μs)

Sm(III) Eu (III) Tb(III) Dy (III)

Ln3+

341 plusmn 1 121 plusmn 25 394 plusmn 19 525 plusmn 1

Ln3+

with

GSH


Ln-DTPA 11 plusmn 1 671 plusmn 4 1930 plusmn 20 14 plusmn 1

0

1

2

3

4

5

6

7

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

160

The luminescence lifetimes of all the metal ions (Table 416) are in the expected

ranges for these ions in aqueous solutions and exhibit the same pattern as the emission

intensities increasing as GSH is added to the metal solutions and being greatest for the

Ln-DTPA complexes The q values were calculated for Eu3+

and Tb3+

as calculations of

q for Sm3+

and Dy3+

are unreliable and were as expected with a hydration number of

around 8 for the M3+

ion in solution co-ordination of around 5 for the M3+

ion with

GSH (consistent with the [GSH] dependence studies in Section 421) and 1 water

molecule bound to the Ln-DTPA complex


and Tb3+

samples at pH 4

Sample Lifetime (μs) q

Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

Ln3+

121 plusmn 25 2309 plusmn 38 394 plusmn 19 1698 plusmn 16 82 82

Ln3+

with

GSH


Ln-DTPA 671 plusmn 4 2066 plusmn 15 1930 plusmn 20 3546 plusmn 27 09 09


As with the dysprosium study extractions were carried out on the mixed

lanthanide samples under the same conditions The aqueous phases contained 005 M

Na5DTPA and 05 M GSH over a pH range of 2-4 The emission spectra of each

aqueous sample before extraction were also recorded but were found to be the same for

each pH The luminescence lifetimes of the samples were also very similar (Table 418)

consistent with the Eu3+

data (Section 422) The q values for Eu3+

and Tb3+

are as

expected with 1 water molecule bound to each Ln-DTPA complex (Table 419) As a

representative example the spectra for the pH 4 sample can be seen in Figure 435

161


10 mM Dy3+

) with

GSH (05 M) and Na5DTPA (005 M) following direct excitation (405 nm for Sm3+

397

nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

Table 418 Luminescence lifetimes for aqueous phases before extraction over a

pH range of 2-4



pH 2 12 plusmn 1 677 plusmn 9 1851 plusmn 21 14 plusmn 1




and Tb3+

samples before



Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

pH 2 677 plusmn 9 2897 plusmn 27 1851 plusmn 21 3765 plusmn 31 09 10



00

10

20

30

40

50

60

70

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

162

The spectra for the aqueous and organic phases after extraction with 10 M

HDEHP in dodecane (in order to ensure sufficient enough extraction to be observed by

this technique) are plotted in Figures 436-438


with 05 M GSH

and 005 M Na5DTPA after extraction with 10 M HDEHP at pH 2 following direct


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

163


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

At all three pH values the order of extractability is Sm gt Eu gt Tb gt Dy

showing that the heavier lanthanides are the most difficult to extract The above data

demonstrate that extraction of Ln3+

is reasonably good at pH 2 and 3 but slightly lower

at pH 3 However at pH 4 extraction of all lanthanide ions is drastically reduced

particularly for Tb3+

and Dy3+

which have very low relative concentrations in the

organic phase Although the extraction of Sm3+

and Eu3+

is also greatly reduced there is

still some extraction of these metals into the organic phase This is consistent with the

previously obtained dysprosium results suggesting that there may be kinetic issues

present for heavier lanthanides at high pH The trend in relative extraction efficiency of

the Ln3+

ions approximately follows the relative stability constants of GSH-Ln

complexes Lighter Ln-GSH complexes are less stable an effect of charge density of the

Ln3+

cations so are extracted more efficiently This was investigated further by ICP-

MS


In order to determine whether a TALSPEAK type system using glutathione as a

buffer had the same kinetic issues as the amino acid systems whereby poor separation of

the heavier lanthanides was observed ICP-MS was carried out on extracted samples

containing 10 lanthanides (La-Ho with the exception of Pm) at pH 2 3 and 4 to

00

05

10

15

20

25

30

35

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

164

determine the distribution pattern of the series using GSH as a buffer The DLn values

can be seen in Figures 439 and 440 for the pH 2 and pH 3 data sets

Figure 439 DLn for varying GSH concentration at pH 2 with 005 M Na5DTPA after




0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

0

5

10

15

20

25

30

35

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

165

The data set for pH 2 resembles a typical TALSPEAK curve as also

demonstrated by amino acids at pH 2 (Section 3) However at pH 3 the distribution of

the metal ions continues to decrease across the lanthanide series indicating that higher

pH is less favourable for extraction of the heavier lanthanides This may be explained

by the fact that the stability of Ln-GSH complexes is lower at lower pH values making

the metal ions easier to extract The analysis was also repeated for samples at pH 4 but

for some of the later lanthanides in the series the quantity of metal ion present was

below the limit of detection of the technique (004 ng mL-1

) so the data could not

accurately be plotted Corresponding separation factors can be seen in Table 420 and

plotted in Appendix 2 (for pH 2 and 3) Separation factors for all lanthanides are fairly

low at pH 2 compared to the original TALSPEAK process (SFEuAm = 91) The data also

show that for the earlier lanthanides as the pH is increased very high separation factors

can be achieved but separation is much lower for later lanthanides with increasing pH

This indicates that unfortunately the same kinetic issues are likely to be a problem at

higher pH for the glutathione buffered system as for the amino acid systems

166

Table 420 SFLnAm for varying GSH concentration over a pH range of 2-4 with

005 M Na5DTPA after extraction with 02 M HDEHP in dodecane

pH

[GSH]

(M)

SF

La Ce Pr Nd Sm Eu Gd Tb Dy Ho

2 01 234 171 148 107 136 158 216 222 237 234

2 02 244 176 145 103 134 146 215 229 239 244

2 03 263 183 145 105 137 165 243 244 281 289

2 04 239 170 151 111 145 168 218 237 259 265

2 05 278 197 164 117 162 189 257 269 300 314

3 01 1735 972 477 276 163 104 112 53 41 38

3 02 1953 841 433 256 320 266 290 130 89 77

3 03 1898 785 388 220 152 90 95 39 28 24

3 04 2046 812 412 243 196 121 126 53 38 34

3 05 2145 705 312 139 36 16 20 04 02 00

4 01 3777 141 12 - - - - - - -

4 02 5548 231 36 06 - - - - - -

4 03 2768 239 27 - - - - - - -

4 04 1620 150 21 01 - - - - - -

4 05 1589 286 48 11 - - - - - -


The glutathione systems were additionally studied by 1H NMR spectroscopy in

order to confirm the complexation observed by luminescence spectroscopy Spectra

were recorded in D2O for GSH GSH after irradiation Eu(NO3)3 with GSH (150)

Na5DTPA with GSH (110) and Eu-DTPA with GSH (1550

Eu(NO3)3Na5DTPAGSH) (Figures 441 a-e)

167

GSH0011resp

45 40 35 30 25 20 15 10


0

005

010

Norm

alized Inte

nsity

197201200100200099

c

d

gb

i

f

44

944

844

6

38

9

37

637

437

2

28

628

628

528

4

24

924

824

724

624

524

4

21

120

920

720

5

GSH Irradiated0011resp

45 40 35 30 25 20 15 10


0

005

010

015

020

025

Norm

alized Inte

nsity

133151244272014101206498131111059100

m

c

d

n

g

q

b

l

i

p

f

47

0

44

7 44

544

442

942

841

641

541

140

940

940

738

137

737

537

3

36

736

6

29

929

728

428

328

1

26

7

24

6

24

424

324

223

823

022

822

6

20

720

520

419

6

19

519

419

319

1

a

b

168

Eu GSH0011resp

45 40 35 30 25 20 15 10


005

010

015

Norm

alized Inte

nsity

035183050206177050088216024026100

d

g

b

i

f

c

45

044

844

7

42

0 41

841

741

341

241

138

0 37

837

737

136

9 30

230

1

28

928

728

628

428

328

1

25

124

924

724

624

424

2 23

3 23

122

921

020

820

720

519

919

819

719

6

GSH DTPA0011resp

45 40 35 30 25 20 15 10


0

005

010

015

Norm

alized Inte

nsity

032158045179156092075366021025099

c

d

g

DTPA

DTPA

DTPA

b

DTPA

i

f

45

044

9 44

744

6

41

941

841

741

241

141

0

37

937

737

537

036

8

34

133

633

5

30

730

530

1

28

928

628

528

428

228

0

25

024

824

624

524

324

1 23

223

022

821

020

820

620

419

719

5

c

d

169

EuDTPA GSH0011resp

45 40 35 30 25 20 15 10


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

180181200200212103673021100

47

0

44

244

1

38

4

36

836

3

32

832

0 30

230

129

9 28

628

528

328

1

24

724

624

524

424

3

20

820

720

520

3

Figure 441 1H NMR spectra for GSH in D2O under a range of conditions at 298 K a)

GSH b) GSH after irradiation with 7 kGy γ-radiation c) Eu(NO3)3 with GSH d) GSH

with Na5DTPA e) Eu-DTPA with GSH

Figure 442 1H

1NMR proton assignments for GSH (top) and γ-Glu-Cys (bottom)

It can be seen from spectra ldquoardquo and ldquobrdquo that there is some degradation of GSH

after irradiation with 7 kGy γ-radiation from a 60

Co irradiator shown by the presence of

e

170

γ-Glu-Cys fragments12

(Figure 442) The buffer seems to be susceptible to γ-radiolysis

and the integration ratios show that the γ-Glu-Cys fragments are present in a significant

quantity as the ratios are comparable to those of the intact GSH Spectrum ldquocrdquo shows

that the buffer does not form a stable complex with Eu3+

as there is only slight shifting

of the peaks indicating weak interaction and perhaps fast dynamic exchange on the

timescale of the NMR experiment There is also no notable paramagnetic broadening as

would be expected if a Eu3+

complex is formed Spectrum ldquoerdquo does show slight

paramagnetic broadening relative to spectrum ldquodrdquo (Na5DTPA with GSH) confirming

the formation of the Eu-DTPA complex seen in previous emission spectra (Section

422)


Since amino acids have not been shown to act as holdback reagents by

themselves the potential of using the tripeptide L-glutathione was investigated Initial

separation studies were carried out using glutathione at pH 4 as is was anticipated that

based on its pKa values glutathione would be most likely to act as a successful

holdback reagent at this pH despite the unfavourable increase of pH Preliminary

investigations found that like amino acids GSH is ineffective as a holdback reagent on

its own as there was no separation observed between Eu3+

and Am3+

when used without

Na5DTPA

Subsequent investigations were carried out using GSH alongside Na5DTPA to

determine whether separation was improved with the tripeptide buffer At pH 2 and pH

3 it was found that the glutathione acts solely as a buffer as the separation factor in each

case was independent of GSH concentration However at pH 4 separation between

Eu3+

and Am3+

was found to increase as the buffer concentration was increased

suggesting that the glutathione is interacting with the Ln-DTPA complexes at this pH

This could be explained by the increase in stability of Ln-GSH complexes as the pH is

increased A buffer concentration of 05 M was then used for all further optimisation

experiments

At 05 M GSH the separation factor was found to increase dramatically as a

function of Na5DTPA concentration up to 03 M Na5DTPA After this peak there was

a rapid decrease in separation as the concentration is increased further up to 06 M

Na5DTPA as the stoichiometry is close to 11 GSHDTPA The separation factors

achieved here were extremely high (~1000) ndash a factor of 10 higher than the current

171

TALSPEAK system and the optimised alanine system whilst still maintaining low Am3+

extraction

At 03 M Na5DTPA the separation factor then increased as the extractant

concentration was increased from 02 to 04 M HDEHP in dodecane after which the SF

began to decrease again with the optimum separation at 04 M giving a SF of 1238 At

04 M Na5DTPA however the separation factor decreases rapidly as the extractant

concentration is increased due to the DAm increasing by a factor of 1000 consistent with

the complexant and buffer possibly forming some kind of adduct which no longer

successfully holds back Am3+

at higher Na5DTPA concentrations

Luminescence experiments mimicking the separation studies showed that the

glutathione does not form a stable complex with the Eu3+

ion and is in exchange with

surrounding solvent molecules even at the highest buffer concentrations preventing the

GSH from acting as a holdback reagent and allowing extraction of the metal into the

organic phase Proton NMR spectroscopy confirmed that although the glutathione may

be in exchange with surrounding water molecules no stable complexes between the

buffer and metal ions are formed (Appendix 8)

In samples containing Na5DTPA a Eu-DTPA complex can be clearly observed

in the emission spectra with or without the presence of GSH over a pH range of 2-4

The J=1J=2 peak ratios showed that there is no change in the co-ordination mode of the

buffer to the metal ion as the concentration of GSH is increased for each pH However

across the data sets the co-ordination mode of glutathione was found to be different at

different pH values as expected based on pKa values and increasing stability constant

with pH

At 05 M GSH the co-ordination mode of the Eu-DTPA complex in the aqueous

phase was found not to change as [Na5DTPA] was changed with metal extraction

typically decreasing as the holdback reagent increases and at 03 M Na5DTPA with 05

M GSH extraction was found to increase as HDEHP concentration increased as

expected Unfortunately luminescence spectroscopy does not seem to be a sensitive

enough technique to gain much information from samples post-extraction using these

conditions


radiolysis a selection of samples were irradiated with 7 kGy γ-radiation and analysed

by luminescence and 1H NMR spectroscopies The radiation was seen to have some

degrading effect on the buffer in the aqueous phase with slightly decreased

luminescence emission intensity of complexes post-irradiation and evidence of

172

significant quantities of γ-Glu-Cys fragments present in the 1H NMR spectrum

However the emission profiles co-ordination mode and luminescence lifetimes of the

samples remained unchanged Extraction also seemed to be unaffected with the

emission remaining relatively constant for each of the phases of the samples after

irradiation

Initial data obtained on the glutathione system with europium(III) and

americium(III) seemed promising as after optimisation very high separation factors

were achieved and despite the buffer being susceptible to radiolysis extraction of

lanthanide ions was still high after irradiation However in order to be a successful

alternative to the current TALSPEAK system it is essential that effective separation of

all lanthanides from MA3+

can occur Further luminescence experiments were carried

out firstly on an analogous dysprosium system in order to represent heavier lanthanide

elements followed by a mixture of 4 lanthanide metals in the same samples

For the dysprosium study as the pH was increased from 2-4 the extraction of

Dy3+

decreased suggesting that the same kinetic issues noted for heavier lanthanides in

the amino acid systems may also be present for the GSH system at higher pH values In

the mixed samples the same pattern was observed with extraction of Ln3+

decreasing as

pH was increased At pH 4 extraction of all lanthanide ions was very low particularly

for Tb3+

and Dy3+

which are both heavier than Sm3+

and Eu3+

ICP-MS was carried out

on a series of samples containing a mixture of 10 lanthanides in order to confirm

whether the heavier lanthanides are in fact subject to kinetic issues with GSH

ICP-MS data was consistent with the luminescence data showing decreased

extraction of heavier lanthanides as pH increases from 2 to 4 The quantity of metal

extracted was so low it was below the limit of detection for some of the heavier metals

at pH 4 forcing the conclusion that unfortunately the same kinetic issues are a problem

at higher pH for the glutathione buffered system as for the amino acid systems Further

optimisation of the system to exploit the combined liquid-liquid extraction efficiencies

as a function of atomic number may allow the development of an extraction process of

lighter over heavier lanthanides for rare earth recycling which is currently a

strategically important goal13

173

1 ImmuneHealthSciencecom What Glutathione (GSH) is and how it affects your

immune health httpwwwimmunehealthsciencecomglutathionehtml 2015

2 ME Sears Scientific World Journal 2013 2013 219840

3 L Patrick Mercury toxicity and antioxidants Part I Role of glutathione and alpha-

lipoic acid in the treatment of mercury toxicity Alternative Medicine 2002

4 EA Bump and JM Brown Pharmacol Ther 1990 47 1 117-136

5 JB Mitchell and A Russo Br J Cancer 1987 55 Suppl VIII 96-104



8 BS Garg BK Singh DN Kumar and PK Sing Indian J Chem 2003 42A 79-83

9 Sigma Aldrich Product Information

httpwwwsigmaaldrichcometcmedialibdocsSigma-AldrichProduct_Information_

Sheetg4251pisPar0001Filetmpg4251pispdf

10 SJA Pope BP Burton-Pye R Berridge T Khan PJ Skabara and S Faulkner

Dalton Trans 2006 2907-2912

11 TS Grimes MP Jensen L Debeer-Schmidt K Littrell and KL Nash J Phys

Chem B 2012 116 46 13722-13730

12 RJ Hopkinson PS Barlow CJ Schofield and TDW Claridge Org Biomol

Chem 2010 8 4915-4920

13 LS Natrajan and MH Langford Paden f-Block Elements Recovery in A Hunt ed

Element Recovery and Sustainability RSC 2013 6 140-184

174

5 MODIFIED DTPA LIGANDS AS COMBINED BUFFERS AND SOFT

DONORS IN A TALSPEAK SYSTEM

Amino acids and the tripeptide L-glutathione have been shown not to be suitable

as a combined buffer and soft-donor for potential replacement of DTPA

(diethylenetriaminepentaacetic acid) and the lactate buffer used in the TALSPEAK

process (Trivalent Actinide Lanthanide Separation by Phosphorus reagent Extraction

from Aqueous Complexation) an advanced reprocessing technique currently being

developed in the USA They do not act as holdback reagents in their own right as they

do not bind preferentially to minor actinide (MA3+

) over lanthanide (Ln3+

) ions

preventing enhanced selective extraction of Ln3+

by HDEHP (di-

(2ethylhexyl)phosphoric acid) into an organic phase The possibility of synthesising a

combined buffer and soft-donor with DTPA and amino acid functionality was therefore

considered

By incorporating additional soft donors onto the DTPA structural framework

from amino acids the overall system would be simplified to just two components rather

than three This could be achieved by incorporating an amino acid or other soft donor

compounds into the DTPA scaffold itself (Figure 51) This strategy may increase the

complexation affinity binding constants and associated thermodynamic parameters to

the MA3+

ion improving the separation and slowing down the kinetics of the exchange

processes if the ligand has a significant specificity for MA3+

over Ln3+

This is

especially true if two of the carboxylic acid moieties are replaced by relatively softer

donors here amide groups

A report on bis(methionine)-appended DTPA was published by Hazari et al in

2010 on the use of Tc-DTPA-bis(methionine) in tumour imaging1 however there are no

literature reports on the synthesis or use of amino acid appended or any modified DTPA

ligands for solvent extraction and separation studies

The work described in this chapter was performed in collaboration with an

MChem student a summer student and the Institute for Waste disposal (INE)

Karlsruhe Germany The initial ligand syntheses were carried out jointly between

myself and the MChem student and all luminescence analysis was performed jointly

The refining of the syntheses and characterisation of the ligands was carried out by a

summer student All separation work using the ligands was carried out by colleagues at

INE

175


51 Ligand Synthesis and Characterisation

A route for the synthesis of DTPA-bis(amino acids) was devised involving ring

opening of the anhydride of DTPA with an amine group of the amino acid in question

whereby the amino acid is incorporated onto two of the side arms of the DTPA

according to Scheme1234

Initially the reaction was attempted using the acid forms of

the amino acid L-alanine however the reaction was found to be unsuccessful since only

an amino acid dimer could be isolated In order to allow optimisation of the reaction

conditions whilst avoiding competitive side reactions the reactions were repeated using

the methyl or ethyl ester protected forms of the amino acids Here commercially

available methyl esters of L-alanine L-arginine and L-histidine and the ethyl ester of L-

serine were used The amide coupling reactions with these amino acid derivatives using

triethylamine as the base proceeded in high yield However isolation and purification of

the products was found to be quite difficult as the reaction products are very

hygroscopic and stubbornly retain residual triethylamine salts Therefore the relatively

impure ligands were isolated for further studies following multiple re-precipitations and

re-crystallisation All the ligands were characterised by 1H NMR spectroscopy

MALDI-MS and elemental analysis (Section 742)

Scheme 1 Synthesis of DTPA-bis(amino) alkyl esters

Protected

Protected Protected

176



The DTPA-amino acid ligands synthesised were studied by luminescence

spectroscopy in a TALSPEAK type system The ligands self-buffer at approximately

pH 2 at 50 mM concentration but to ensure consistency in studies the pH of systems

were adjusted to exact pH values (plusmn 01) Aqueous phases were prepared containing 50

mM ligand and 1 mM Eu(NO3)3 at pHpD 2 3 and 4 for each of the four synthesised

ligands Samples were measured in D2O and H2O The emission spectra of the D2O

samples can be seen in Figures 52-54 The spectra for the samples in H2O are identical

but with lower relative emission intensities

Figure 52 Emission spectra of Eu(NO3)3 with DTPA-bis(amino ester) ligands in D2O

at pD 2 following excitation at 397 nm

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

177





The emission spectra are all very similar and show clear complexation of the

Eu3+

ion with each ligand There is little difference in emission intensity and form of the

spectra across all of the samples which indicates that all of the ligands present the same

coordination environment to the Eu3+

centre as expected

Table 51 J=1J=2 peak ratios and t-test results for Eu- DTPA-bis(amino ester)

complexes at pD 2-4

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

0

5

10

15

20

25

30

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

178

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pD 2 0359 0381 0404 0353 0023

No sig

diff

pD 3 0394 0425 0417 0381 0020

No sig

diff

pD 4 0391 0427 0432 0423 0019

No sig

diff

st dev 0019 0026 0014 0035

t-test No sig

diff

No sig

diff

No sig

diff

No sig

diff




data set the range in the ratios is small and there is no significant difference between

the values again suggesting that the co-ordination mode of the each of the ligands to the

metal ion is the same Across the data sets unlike the glutathione system (Chapter 4)

no significant difference was observed either as pD increases from pD 2 to pD 4

indicating that the co-ordination mode of the complexes is not changing with pH




179

Table 52 Luminescence lifetimes and q values for Eu-DTPA-bis(amino ester)

complexes at pD 2-4 recorded at the emission maximum (617 nm) following 397 nm

excitation

pH amp Ligand τ D2O (μs) τ H2O (μs) q plusmn 02

pH 2 DTPA-(AlaOMe)2 1794 plusmn 7 587 plusmn 8 09

pH 2 DTPA-(ArgOMe)2 1828 plusmn 12 626 plusmn 10 08

pH 2 DTPA-(HisOMe)2 1816 plusmn 10 614 plusmn 9 09

pH 2 DTPA-(SerOEt)2 1759 plusmn 9 563 plusmn 11 10










hydration sphere This is consistent with the formation of a Eu-DTPA-amide ligand

complex The values are generally slightly less than 1 in contrast to [Eu-DTPA]2-

itself

where q = 11 indicating the likely fast exchange of the bound water molecule with

other surrounding water molecules and that the amino ester appendage may inhibit the

close approach of more than one water molecule due to steric reasons




post-extraction can be seen in Figures 55-58

180


extraction from an aqueous

phase containing DTPA-bis(amino ester) ligands (50 mM) at pH 2 following excitation

at 397 nm


extraction from

an aqueous phase containing DTPA-bis(amino ester) ligands (50 mM) at pH 2


0

0

0

0

0

1

1

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

0

10

20

30

40

50

60

70

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq Arg-DTPA Aq His-DTPA Aq Ser-DTPA Aq Ala-DTPA Org Arg-DTPA Org His-DTPA Org Ser-DTPA Org

181


extraction from




extraction from



0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


0

1

2

3

4

5

6

7

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

Ala-DTPA Org

Arg-DTPA Org

His-DTPA Org

Ser-DTPA Org

182


Eu-DTPA complexes in the aqueous phase as can be seen be the different profile of the

emission spectra of the organic phases The extraction data show that the best Eu3+

extraction occurs at pH 2 under these conditions as there is complete metal extraction

into the organic phase for all of the ligands and very little or no metal remaining in the

aqueous phase Above pH 2 the extraction of Eu3+

decreases leaving some of the metal

ion in the aqueous phase at pH 3 and an even higher proportion at pH 4 At pH 3

extraction is relatively higher with the DTPA-(SerOEt)2 ligand than any of the other

ligands and at pH 4 extraction is higher with DTPA-(HisOMe)2 and DTPA-(ArgOMe)2

The J=1J=2 peak ratios for the organic phases (Table 53) show no significant

difference in co-ordination mode within the pH 2 or pH 4 data for each ligand however

the co-ordination can be seen to change slightly with each ligand at pH 3 Also no

significant difference is observed as pH is changed for DTPA-(ArgOMe)2 and DTPA-

(AlaOMe)2 however there is a significant difference observed for DTPA-(SerOEt)2 and

DTPA-(HisOMe)2 as pH is changed Each emission spectrum was recorded 5 times and

an average taken and repeat measurements were also taken so whilst the data is

reproducible it appears to be inconsistent and difficult to explain without further

investigation into the co-ordination environment at different pH values by means other

than luminescence spectroscopy although it can be seen that pH 2 is optimum for

extraction using these ligands

Table 53 J=1J=2 peak ratios and t-test results for organic phases after extraction after

Eu3+

extraction aqueous phases containing DTPA-bis(amino ester) ligands (50 mM) at

pH 2-4

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pH 2 0208 0207 0198 0208 0005 No sig diff

pH 3 0210 0213 0311 0347 0069 Sig diff

pH 4 0182 0210 0206 0205 0013 No sig diff

st dev 0016 0003 0063 0081

t-test No sig diff No sig diff Sig diff Sig diff

183



In order to determine how resistant the ligand are to radiolysis a selection of

samples at pHpD 2 containing 50 m M ligand and 1 mM Eu(NO3)3 were irradiated at

the Dalton Cumbrian Facility using a 60

Co irradiator The samples were exposed to 7

kGy γ-radiation and analysed by luminescence spectroscopy The emission spectra of

the D2O samples can be seen in Figure 59 The spectra for the samples in H2O are the

same but with lower emission intensity

Figure 59 Emission spectra of Eu(NO3)3 in D2O with DTPA-bis(amino ester) ligands

(50 mM) at pH 2 after irradiation with 7 kGy γ-radiation and following excitation at

397 nm

The spectra of the samples are the same after irradiation as beforehand

indicating that the radiation has little or no degrading effect on the complexes in the

aqueous phase The J=1J=2 ratios and co-ordination mode remained unchanged (Table

54) as do the luminescence lifetimes and q values of the samples (Table 55)

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

184

Table 54 J=1J=2 peak ratios and t-test results for Eu-DTPA-bis(amino ester)

complexes at pD 2 after irradiation with 7 kGy γ-radiation

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2 st dev t-test

J=1J=2 0357 0395 0412 0362 0026 No sig

diff


complexes at pD 2-4 after irradiation with 7 kGy γ-radiation

Ligand τ D2O (μs) τ H2O (μs) q plusmn 02

DTPA-(AlaOMe)2 1818 plusmn 7 613 plusmn 8 09

DTPA-(ArgOMe)2 1843 plusmn 12 586 plusmn 10 10

DTPA-(HisOMe)2 1803 plusmn 10 629 plusmn 9 08

DTPA-(SerOEt)2 1809 plusmn 9 598 plusmn 11 09


Extractions were then carried out on some of the irradiated samples using 06 M

HDEHP in dodecane The emission spectra of both the aqueous and organic phases



extraction from

an irradiated (7 kGy γ-radiation) aqueous phase containing DTPA-bis(amino ester)


0

1

2

3

4

5

6

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq Arg-DTPA Aq His-DTPA Aq Ser-DTPA Aq Ala-DTPA Org Arg-DTPA Org His-DTPA Org

185

The emission profiles of the samples are the same after irradiation as

beforehand indicating that the radiation has little or no degrading effect on the

complexes in the aqueous phase The emission intensity is lower for the organic phases

after irradiation than beforehand possibly due to increased quenching effects caused by

radicals present as a result of irradiating the solvents The J=1J=2 ratios and co-

ordination mode for the organic phase remained unchanged (Table 56) and the

luminescence lifetimes can be seen to decrease only slightly after irradiation consistent

with the decrease in emission intensity (Table 57)

Table 56 J=1J=2 peak ratios and t-test results for the organic phases after Eu3+

extraction from aqueous phases containing DTPA-bis(amino ester) ligands (50 mM) at

pH 2 one of which had been irradiated with 7 kGy γ-radiation

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

J=1J=2 0241 0233 0198 0231 0019

No sig

diff

Table 57 Luminescence lifetimes and q values for the organic phases after Eu3+



Ligand τ organic phase

without irradiation

(micros)

τ organic phase after

irradiation

DTPA-(AlaOMe)2 2151 plusmn 21 1829 plusmn 18

DTPA-(ArgOMe)2 1881 plusmn 19 1821 plusmn 17

DTPA-(HisOMe)2 2265 plusmn 18 2227 plusmn 18

DTPA-(SerOEt)2 1856 plusmn 20 1777 plusmn 19


Some separation work using these ligands was carried out with the help of

Andreas Geist at KIT-INE in Germany Extractions were performed under TALSPEAK

conditions but using kerosene as the organic phase due to availability

186


A stock spiking solution of 241

Am + 152

Eu (1 kBq mL-1

) was added to a solution

of yttrium and lanthanides (10 mgdm3 of each Ln(NO3)3) with each ligand (50 mM) for

DTPA-(ArgOMe)2 DTPA-(SerOEt)2 DTPA-(HisOMe)2 at pH 1-2 The aqueous phases

were contacted with HDEHP (02 M) in kerosene and shaken for 30 minutes The

phases were then separated and the Am3+

and Eu3+

concentrations in each phase were

determined by Gamma counting The separation factors for all ligands under these

conditions were found to be approximately 100 across the pH range measured Graphs

of these data are plotted in Figures 511-513 These values are comparable with the

original TALSPEAK process using lactate (SF = 91) Although the TALSPEAK

process uses dodecane rather than kerosene and as such the results are therefore not

directly comparable they still show selectivity between Am3+

and Eu3+

for these

ligands However the DAm using these ligands is 2-3 orders of magnitude higher than in

the original TALSPEAK process (~025-200 compared to 0009) indicating that Am3+

is not being held back sufficiently by the ligand for this to be a viable process and that

more work is needed to decrease the partitioning of Am3+

into the organic phase This

may be possible with optimisation of the systems by varying the pH concentration of

ligand concentration of extractant and by modifying the solubility of the ligands ie by

cleavage of the methyl and ethyl ester groups to generate the amino acid Nevertheless

these results are particularly encouraging


Am3+

using DTPA-

(ArgOMe)2 (005 M) at pH 1-2 extracted using HDEHP (02 M) in kerosene

187


Am3+

using DTPA-

(SerOEt)2 (005 M) at pH 1-2 extracted using HDEHP (02 M) in kerosene


Am3+

using DTPA-

(HisOMe)2 (005 M) at pH 1-2 extracted using HDEHP (02 M) in kerosene


In addition to the Eu3+

Am3+

separation studies carried out at KIT-INE using

these amino ester appended DTPA ligands further experiments were conducted to

observe the separation across the lanthanide series by ICP-MS under the same

conditions The graphs of the distribution ratios for each Ln3+

and Am3+

can be seen in

Figures 514-516 for each ligand as well as the separation factor for Nd3+

Am3+

(as

188

Nd3+

is the most difficult lanthanide to extract) The SFNdAm in each case is 30-40 over

the pH range 1-2 These separation factors are good only slightly lower than the

original lactate-buffered TALSPEAK process (SFNdAm ~ 55) and the distribution ratios

for the heavier lanthanides are particularly high higher than the original process with a

greater proportion of them having D values of over 1000 (Figures 514-516)


using DTPA-(ArgOMe)2 (005 M) at pH 1-2

extracted using HDEHP (02 M) in kerosene

189


using DTPA-(SerOEt)2 (005 M) at pH 1-2



using DTPA-(HisOMe)2 (005 M) at pH 1-2


190

55 Summary and Conclusion of Modified DTPA Ligand Work

After initial difficulties synthesising amino acid appended DTPA ligands the

ligands were successfully synthesised in good yields (~60 ) for DTPA-(AlaOMe)2

DTPA-(ArgOMe)2 DTPA-(SerOEt)2 and DTPA-(HisOMe)2 using ester protected

versions of the amino acids The ligands were shown by luminescence spectroscopy to

complex to Eu3+

at pH 2 3 and 4 forming Eu-DTPA-bis(amino ester) adduct with 1

water molecule in fast exchange in the inner hydration sphere Under TALSPEAK

conditions the ligands were found to be more effective holdback reagents at the lower

pH of 2 but also effectively extract Eu3+

over Am3+

as low as pH 15 This is in stark

contrast to the original TALSPEAK process The co-ordination mode of the ligands to

the metal ion was consistent for all of the ligands but was found to change slightly upon

changing pH although the overall coordination number of Eu3+

with the ligands

remained as approximately 8 (with the 9th

coordination site being completed by one

water molecule) Studies showed that the ligands are relatively resistant to radiolysis

when subjected to 7 kGy γ radiation as there was no change in their luminescence

emission profile co-ordination mode or hydration number after irradiation

Results from separation studies conducted at KIT-INE using gamma counting

and ICP-MS showed that the modified DTPA ligands successfully allowed separation

between Ln3+

Am3+

giving good separation factors comparable to the original lactate-

buffered TALSPEAK process (SFEuAm ~100) even for Nd3+

which is the most difficult

lanthanide to extract in the process (SFNdAm ~30-40) The extraction efficiency of all the

ligands broadly relates to the atomic number of the lanthanide ions (apart from La3+

Ce3+

and Pr3+

) with the heavier ions being preferentially extracted as expected The

separation factors of individual lanthanide pairs range from approximately 25 to gt 100

and for the Dy3+

Nd3+

pair of particular economic importance are quite reasonable SF

DyNd ~ 30

However the distibution ratio for Am3+

is higher than desired (025-200 vs

0009) and so optimisation of the systems would be necessary to try to reduce DAm for

the combined buffer soft-donor system to be viable Another step would also be to try to

deprotect the amino acids on the ligands hydrolysing the esters back to carboxylic acid

groups to see if that would increase the holdback ability of the ligands and possibly

decrease the distribution ratio of Am3+

191

1 PP Hazari G Shukla V Goel K Chuttani N Kumar R Sharma and AK Mishra

Bioconjugate Chem 2010 21 229-239

2 X Wang X Wang Y Wang and Z Guo Chem Comm 2011 47 8127-8129 ESI

3 SJ Pope BJ Coe S Faulkner and R H Laye Dalton Trans 2005 1482-1490

4 S J Pope B J Coe and S Faulkner Chem Commun 2004 1550-1551

192

6 SUMMARY CONCLUSIONS amp FUTURE WORK


One technique for reprocessing SNF currently being developed in the USA is

the TALSPEAK process an advanced reprocessing method for the separation of Ln3+

and MA3+

components The traditional process developed in the 1960s uses DTPA to



allowing Ln3+


phase of DIPB or dodecane TALSPEAK is one of the most promising techniques being

researched due to its numerous advantages particularly its relative resistance to

irradiation and ability to be carried out without the need for high reagent concentrations

Additionally it gives high separation factors in the region of ~50-100 which is

comparable to other advanced reprocessing methods currently being developed1 Since

the chemistry of the process is very complex and not particularly well understood it

would be an advantage to simplify the process by removing the need for a separate

holdback reagent and buffer

Recent studies have shown that complexants with soft donor atoms such as N or

S (relative to O) can be used to separate MA3+

from Ln3+

23

Initial research was carried

out by our collaborators at the Idaho National Lab testing the suitability of amino acids

(L-alanine L-arginine L-histidine and L-methionine) as a potential combined buffer

and soft donor by determining whether amino acids preferentially bind to MA3+

Another benefit to using amino acids would be the scope for carrying out the process at

a lower pH (~ pH 2) due to the lower pKa values of the carboxylic acid groups of the

amino acids than on DTPA Lower pH values are preferred by industry as higher acid

concentrations are easier to control on a large scale and are also known to increase the

Ln3+

distribution coefficients4

This work carried out by Grimes5 showed that amino acids do not act as

holdback reagents in their own right and that no separation of Ln3+

Am3+

is achieved

when they are used without Na5DTPA in solution However investigations showed that

when used alongside Na5DTPA good separation (SFEuAm ~ 66) can be achieved when

using 05 M L-alanine at pH 2 (cf ~25 at pH 3) however the DAm value was relatively

high than at the lower pH (DAm 047 at pH 2 cf 012 at pH 3) as more protonated forms

of the DTPA molecule are present in solution at low pH and the holdback reagent is not

able to bind as strongly to metal ions allowing more Am3+

to be partitioned into the

organic phase

193

However optimisation of the system in order to maximise the separation whilst

keeping Am3+

partitioning to a minimum by changing the concentrations of holdback

reagent and extractant proved to be successful The optimum conditions were found to

be 04 M Na5DTPA and 02 M HDEHP giving a separation factor of 71 plusmn 5 with a DAm

value of 008 Although this separation is not as good as a traditional lactate

TALSPEAK system (SF = 91 DAm = 0009) the use of L-alanine (pKa = 235) as a

buffer would allow the process to be carried out at pH 2 which is a much more

preferable pH for industry

Separations were carried out using other amino acids at varying pH values and it

was found that L-methionine was too poorly soluble at pH 3 and did not give very good

separation data at pH 2 L-arginine was found to have kinetic issues at pH 2 and 3

giving poor separation of the heavier lanthanides The amino acid L-histidine (pKa =

182) however gave good separation data at pH 3 with a SFEuAm of 99 comparable to

that of the original TALSPEAK process and a DAm of 007 comparable to the optimised

L-alanine system Unfortunately ICP-MS studies on lanthanides La-Ho using L-

histidine at pH 3 showed that the same kinetic problems arise for this system as for L-

alanine at pH 3 and L-arginine at pH 2 and 3 as the DLn value decreases for later

lanthanides

The interaction of the buffers glycine L-alanine L-serine L-phenylalanine and

lactate (for comparison) with Eu3+

and [Eu(DTPA)]2-

systems was investigated by

luminescence and 1H NMR spectroscopies As expected it was found that amino acids


DTPA complex and that the buffers are likely to be in fast exchange with surrounding

solvent molecules as the number of water molecules in the inner hydration sphere (q) of

Eu3+

was reduced from 9 to ~6 when buffers were added to the aqua ion in solution

Luminescence studies on L-phenylalanine (like other amino acids) showed that it does


ion when



and Cm3+


DTPA complexes showed no change in emission profile upon the addition of amino

acidslactate There was also no change in q when buffers were added to metal-DTPA

complexes in solution for Eu3+

or Cm3+

Radiolysis studies carried out on lactate and amino acid buffered [Eu(DTPA)]2-

systems showed that the systems are relatively resistant to γ-radiation when exposed to

5 kGy γ-radiation This is consistent with previous work conducted by the INL showing

194

that separation systems using L-alanine as a buffer are more resistant to radiolysis than

the original TALSPEAK process using lactate67

A 05 M L-alanine buffered

TALSPEAK system using 04 M Na5DTPA and 02 M HDEHP at pH 2 can therefore

be seen to be a promising alternative to the traditional lactate buffered system as it has

been shown to give good separation data with fairly low extraction of Am3+

and the

buffer is also more resistant to radiolysis than lactate Additionally it allows the process

to be carried out at a lower pH of 2 which is much more practical for industrial

operation

Since amino acids were found not to act as holdback reagents in their own right

the potential of using the larger tripeptide L-glutathione (GSH) was investigated Initial

separation studies carried out using glutathione at pH 4 (as GSH has 2 pKa values

below 4 and Garg et al reported that the optimum stability for Ln-GSH complexes

occurs in solutions between pH 34-348)8 Preliminary investigations found that as

with the amino acids studied GSH is ineffective as a holdback reagent on its own as

there was no separation observed between Eu3+

and Am3+

when used without

Na5DTPA

Analogous to the amino acid studies subsequent investigations were carried out

using GSH alongside Na5DTPA to determine whether separation was improved with the

tripeptide buffer A pH dependence study found that at pH 2 and pH 3 the glutathione

acts solely as a buffer in the systems as the separation factor in each case was

independent of GSH concentration However at pH 4 interestingly separation between

Eu3+

and Am3+

was found to increase as the buffer concentration was increased up to

05 M suggesting that the glutathione is interacting with the Ln-DTPA complexes at

this pH This could be explained by the increase in stability of Ln-GSH complexes as

the pH is increased

Using 05 M GSH the separation factor was found to increase dramatically as a


a rapid decrease in separation as the concentration was increased further up to 06 M



TALSPEAK system and the optimised L-alanine system whilst still maintaining low

Am3+

extraction (DAm = 0002 with 03 M Na5DTPA) lower than in the traditional

TALSPEAK process



195

began to decrease again with the optimum separation at 04 M extractant giving a SF

of 1238 (DAm = 00018) At 04 M Na5DTPA however the separation factor decreases

rapidly as the extractant concentration is increased due to the DAm increasing by a

factor of 1000 consistent with the complexant and buffer possibly forming an adduct






surrounding solvent molecules comparable to the amino acid buffer studies even at the

highest buffer concentrations 1H NMR spectroscopy confirmed that although the

glutathione may be in exchange with surrounding water molecules no kinetically stable

complexes between the buffer and metal ions are formed In samples containing

Na5DTPA a Eu-DTPA complex can be clearly observed in the emission spectra with

or without the presence of GSH over a pH range of 2-4 The J=1J=2 peak ratios

showed that there is no change in the co-ordination mode of the buffer to the metal ion

as the concentration of GSH is increased for each pH however across the data sets the

co-ordination mode of glutathione was found to be different at different pH values as

expected based on pKa values and increasing stability constant with pH

The co-ordination mode of the Eu-DTPA in the aqueous phase with 05 M GSH

was found not to change as [Na5DTPA] was changed with metal extraction typically

decreasing as the holdback reagent increases and at 03 M Na5DTPA with 05 M GSH

extraction was found to increase as HDEHP concentration increased as expected

The GSH buffered system was found to be susceptible to radiolysis when

subjected 7 kGy γ-radiation from a 60

Co irradiator and seen to degrade into γ-Glu-Cys

fragments However the degradation was seen to have little effect on the extraction of

metal ions from the aqueous phase when analysed by luminescence spectroscopy with

only slightly decreased emission intensity post-irradiation The emission profiles co-

ordination mode and luminescent lifetimes of the samples remained unchanged

In order to be a successful alternative to the current TALSPEAK system it is

essential that effective separation of all lanthanides from MA3+

can occur Further

luminescence experiments were carried out firstly on analogous dysprosium systems in

order to represent heavier lanthanide elements followed by a mixture of four different

lanthanide metals in the same samples (Sm3+

Eu3+

Tb3+

and Dy3+

) For the dysprosium

study as the pH was increased from 2-4 the extraction of Dy3+

decreased suggesting

that the same kinetic issues noted for heavier lanthanides in the amino acid systems may

also be present for the GSH system at higher pH values In the mixed samples the same

196

pattern was observed with extraction of Ln3+

decreasing as pH was increased At pH 4

extraction of all lanthanide ions was very low particularly for Tb3+

and Dy3+

which are

both heavier than Sm3+

and Eu3+

ICP-MS carried out on a series of samples containing

a mixture of 10 lanthanides (La3+

-Ho3+

) was consistent with the luminescence data

showing decreased extraction of heavier lanthanides as pH increases from 2 to 4 The

quantity of metal extracted was so low it was below the limit of detection for some of

the heavier metals at pH 4 forcing the conclusion that unfortunately the same kinetic

issues are a problem at higher pH for the glutathione buffered system as for the amino

acid systems


americium(III) seemed promising as after optimisation very high separation factors for

Eu3+

Am3+

were achieved (~1000) with very low Am3+

partitioning (DAm ~0002) and

although the buffer was found to be susceptible to radiolysis extraction of lanthanide

ions still remained high after irradiation However subsequent studies with heavier

lanthanides showed that the GSH buffered system is subject to the same kinetic

problems as some of the amino acid systems

Based on the results from studies using amino acid and glutathione buffered

systems demonstrating that Ln3+

MA3+

separation cannot be achieved without the

presence of DTPA and a buffer the possibility of synthesising a combined buffer and

soft-donor was considered Amino acids were appended onto DTPA through reaction of

amino acid esters with DTPA dianhydride to form DTPA-(AlaOMe)2 DTPA-

(ArgOMe)2 DTPA-(SerOEt)2 and DTPA-(HisOMe)2 in good yields (~ 60 ) The

ligands were shown by luminescence spectroscopy to complex to Eu3+

at pH 2 3 and 4

forming Eu-DTPA-AA2 adducts with 1 water molecule in fast exchange in the inner

hydration sphere Under TALSPEAK conditions the ligands were found to be more

effective holdback reagents at the lower pH of 2 and even at pH 15 The co-ordination

mode of the ligands to the metal ion was consistent for all of the ligands being typical

of lanthanide DTPA-amide ligands known in the literature910

but was found to change

upon changing pH These ligands were also found to be relatively resistant to radiolysis

when subjected to 7 kGy γ radiation from a 60

Co irradiator as there was no change in

their luminescent emission profile co-ordination mode or hydration number after

irradiation



between Ln3+

Am3+


197





Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30


is much higher than desired for the

modified DTPA ligands (DAm = 025-200 vs DAm 0009) and so optimisation of the

systems would be necessary to try to reduce DAm for the combined buffer soft-donor

system to be viable Initial studies on combined DTPA-bis(amino ester) ligands is

promising allowing the TALSPEAK process chemistry to be simplified and providing a

system which could be buffered to a lower pH (pH 2) as preferred by industry The

synthesis of the ligands is quite moisture sensitive and the products are very

hygroscopic and difficult to purify making the application of them on an industrial

scale potentially problematic but the simplification of the process on a laboratory scale

would allow the chemistry of the TALSPEAK process to be further investigated and

better understood for future developments

Although there are a number of variations of the TALSPEAK process being

developed including the TALSQuEAK (Trivalent Actinide Lanthanide Separation

using Quicker Extractants and Aqueous Complexes) process11

which uses alternative

extractant HEH[EHP]12

and alternative holdback reagent HEDTA13

the use of amino

acid and short-chain peptide buffers is unique to this project in collaboration with the

Idaho National Laboratory There has been some investigation into the use of malonate

buffers for TALSPEAK14

but there are no other reports of the use of amino acids or

peptides in the literature Additionally there are few published reports on the use of

luminescence spectroscopy in TALSPEAK studies chiefly on the complexation of Eu3+

with lactate15

complexation of Eu3+

Cm3+

with DTPA16

and complexation of Eu3+

with

HDEHP in the organic phase17

There is no literature on systems as a whole


2010 on the use of Tc-DTPA-bis(methionine) in tumour imaging18

however there are

no literature reports on the synthesis or use of amino acid appended or any modified

DTPA ligands for solvent extraction and separation studies

198

62 Future Work

As only a small selection of amino acids have been tested as buffers it would be

interesting to try more of them The original selections were made on the basis of their

chemical structures solubilities and previous work conducted at INL plus presence of

any soft donor atoms L-alanine was selected as it has the most similar structure to lactic

acid although glycine may be worth considering as well based on its also very similar

structure and high aqueous solubility Results with L-arginine and L-methionine were

not very promising possibly due to their longer chain backbones so it may be worth

considering the similar shorter-chain amino acids L-cysteine and L-threonine as these

have similar structures to L-serine which along with glycine was one of the amino

acids investigated by luminescence spectroscopy Although L-cysteine has poor

solubility like L-methionine it would be interesting to see how these amino acids

behave as buffers when subjected to the same separation and optimisation tests as L-

alanine Similarly medium length chain amino acids L-glutamic acid L-aspartic acid

L-asparagine and L-glutamine may also be worth considering (Figure 61)

Figure 61 Chemical structures of amino acids taken from reference 1919

199

In addition to investigating other amino acid buffer systems as discussed in

Chapter 4 there may be some benefit to carrying out experiments with other short chain

peptides such as eisenin and norophthalmic acid as well as some of the B vitamins that

were considered (vitamins B7 and 9) before L-glutathione was selected From the

results obtained with L-glutathione demonstrating that the tripeptide interacts with the

Ln-DTPA complex under certain conditions it is possible that these other peptides may

also interact and potentially aid in extraction of Ln3+

or selective holdback of MA3+

Although the desired result was not achieved with L-glutathione as it seems to

suffer the same kinetic issues which have been common with amino acids causing very

good extraction of the lighter lanthanides but very poor extraction of the heavier

lanthanides further optimisation of the GSH system to exploit the combined liquid-

liquid extraction efficiencies as a function of atomic number may allow the

development of an extraction process of lighter over heavier lanthanides for rare earth

recycling which is currently a strategically important goal20

Initial studies on the modified DTPA ligands showed promising results for a

combined buffer and soft-donor although there is still much work to be done in this

area It would be useful to determine the stability constants of the ligands with

lanthanides and with Am3+

and Cm3+

if possible preferably by potentiomenty which

has proven to be the most reliable method for determining stability constants for these

types of complexes21

The next step in process development with the ligands would be

to optimise the systems (as was done for the L-alanine and GSH buffered systems) in

order to reduce the partitioning of Am3+

and decrease DAm as much as possible ideally

to the same of magnitude of the lactate and GSH buffered systems by altering pH

concentration of ligand and concentration of extractant to maximise separation and

minimise americium distribution

A further step would also be to try to deprotect the amino acids on the DTPA-

amino ester ligands hydrolysing the esters back to carboxylic acid groups to see if that

would increase the holdback ability of the ligands and possibly decrease the distribution

ratio of Am3+

It is envisioned that the research presented in this thesis could be applied to

current and new technologies and challenges faced in the future of the nuclear industry

in particular towards the development of a TALSPEAK-style advanced reprocessing

procedure for implementation in the USA within the near future

200

1 G Modolo A Geist and M Miguirditchian Minor actinide separations in the

reprocessing of spent nuclear fuels recent advances in Europe in R Taylor ed

Reprocessing and Recycling of Spent Nuclear Fuel Woodhead Publishing UK 2015

10 245-279


3 L R Martin B J Mincher and N C Schmitt J Radioanal Nucl Chem 2009 282

523-526






2014 32 378-390




9 C L Davies N G Housden and A-K Duhme-Klair Angew Chem Int Ed Engl 2008

47 8856

10 SJA Pope Polyhedron 2007 26 17 4818-4824

11 JC Braley JC Carter SI Sinkov KL Nash and GJ Lumetta J Coord Chem

2012 65 16 2862-2876

12 GJ Lumetta AJ Casella BM Rapko TG Levitskaia NK Pence JC Carter

CM Niver and MR Smoot Solv Extraction Ion Exchange 2015 33 346-361

13 JC Braley TS Grimes and KL Nash Ind Eng Chem Res 2012 15 629-638

14 JL Lapka and KL Nash Solv Extraction Ion Exchange 2015 33 346-361




18 PP Hazari G Shukla V Goel K Chuttani N Kumar R Sharma and AK

Mishra Bioconjugate Chem 2010 21 229-239

19 DWhite Wisegeek What are Amino Acids httpwwwwisegeekorgwhat-are-

amino-acidshtm 2015




201

7 EXPERIMENTAL SECTION


All chemicals and solvents were purchased from Sigma-Aldrich chemical

company and were used as received Radioisotopes were supplied by the Idaho National

Laboratory or the Institute for Nuclear Waste Disposal (INE) and were used in

accordance with the local rules for manipulation of high specific activity materials


In order to handle radioisotopes at INL it was necessary to compete the

RadWorker 2 training and theory and practical examinations Upon entering a radiation

area (laboratory) it was a requirement to sign onto the dosimetry record system and

collect a dosimeter which was to be worn on the chest at all times in the area When

handling radioactive material within the designated controlled areas (fume hoods) extra

layers of PPE (personal protective equipment) such as triple layered shoulder length

gloves were to be worn and disposed of immediately upon leaving the controlled area in

designated radioactive waste bins It was then a requirement to monitor the upper body

area carefully with an alpha and a beta radiation detector Whilst working in the

controlled area any potentially contaminated PPE or samples had to be disposed of and

immediately replaced in the case of PPE After preparing sealed samples in the

controlled areas a Radiological Control worker would assist with swabbing each

sample to check for contamination before it could be removed from the area for further

analysis Samples were not to be opened outside of controlled areas and were returned

to the controlled area fume hood to be disposed of by solidification Upon leaving

radiation areas a full body scan was conducted and dose records updated as dosimeters

were returned


amp An3+

with amino acids in TALSPEAK systems



Stock solutions (10 mM 10 mL) were made up for each lanthanide (EuTb)

using the corresponding lanthanide nitrate salt Ln(NO3)3xH2O in H2O or D2O as

required A stock solution of Na5DTPA in H2OD2O (1 M 50 mL) was made up from a

40 wv Na5DTPA solution in H2O by dilution (2517 g into 50 mL) Stock solutions

of amino acids (Gly L-Ala L-Ser) in H2OD2O (125 M 20 mL) were prepared from

202

the crystalline form of each amino acid and a stock solution of DL-lactic acid was

prepared by dilution (225 g in 20 mL) For the sensitisation study with L-Phe due to

poor solubility of L-Phe a 0625 M stock solution in D2O was made using the powdered

form of the amino acid Additionally a stock solution of HDEHP in n-dodecane (645 g

in 100 mL 02 M) was prepared All reagents were purchased from Sigma-Aldrich

Stock solutions

10 mM EuTb(NO3)3 in H2OD2O

1 M Na5DTPA in H2OD2O

125 M GlyL-AlaL-SerLactate in H2OD2O

0625 M L-Phe in D2O

02 M HDEHP in n-dodecane


5 mL samples were prepared using the stock solutions above Ln(NO3)3xH2O

(05 mL) was added to each amino acid solution (4 mL) with either Na5DTPA solution

(05 mL) or H2OD2O (05 mL) depending on whether the samples contained DTPA

This produced individual samples with concentrations of 1 mM Ln3+

1 M amino

acidlactate (05 M for L-Phe) and 01 M Na5DTPA if applicable The pHpD of

samples was adjusted individually with concentrated HNO3 and NaOH to minimise

change in volume using a Mettler Toledo Seven Compact pHion Meter pD (-log10

deuterium ion concentration) was calculated using Equation 71 to account for the

activity coefficient difference between the different isotopes of the hydrogen ion where

pH = the meter reading from a calibrated pH electrode All samples were repeated in

triplicate analagous to the solvent extraction samples performed at INL

Equation 71


Aqueous samples were prepared using the stock solutions above Na5DTPA

solution (05 mL) was added to amino acid solution (4 mL) and the mixture was pre-

equilibrated by contacting with n-dodecane and shaken using a Scientific Industries

Vortex Genie 2 Mixer and Shaker for 15 minutes The phases were allowed to separate

and the organic layer was discarded Ln(NO3)3 solution (05 mL) was added to the

aqueous phase and the pH was adjusted individually with concentrated HNO3 and

NaOH to minimise change in volume using a Mettler Toledo Seven Compact pHion

203

Meter The pD was calculated using Equation 71 The aqueous phases were contacted

with HDEHP in n-dodecane (5 mL 02 M) The solutions were then shaken again for 15

minutes left to settle and separated into the two phases for analysis All samples were

repeated in triplicate analagous to the solvent extraction samples performed at INL


Fricke dosimetry can be used to determine dose rates from radiation sources

such as from a 60

Co irradiator used to irradiate samples for radiolysis studies at the

Dalton Cumbrian Facility An aerated iron(II) sulphate solution is irradiated to give free

radicals according to the following reactions

H2O rarr H + OH

OH + Fe2+

rarr Fe3+

+ HO-

H + O2 rarr HO2

H+ + Fe

2+ + HO2 rarr Fe

3+ + H2O2

H2O2 + Fe2+

rarr Fe(OH)2+

+ OH

HO2 + Fe3+

rarr Fe2+

+ O2 + H+

This means that each H radical causes the oxidation of 3 Fe2+

ions to Fe3+

The amount

of Fe3+

present can then be measured using UV-visible spectroscopy and the dose rate

calculated from this1


A Fricke solution was needed for the first set of radiolysis experiments carried

out using the 60

Co irradiator at the DCF as it allows the amount of exposure to be

calculated for each sample position during irradiation

FeSO47H2O (020206 g 133 mM) NaCl (003031 g 052 mM) and H2SO4 (95-98

11 mL) were added to deionised water (500 mL) The resulting Fricke solution was

then air-saturated and stored away from natural and artificial light sources


The UV-vis spectra of Fricke solution was then read before and after irradiation

and the following equation used to work out the dose rate

The dose can be calculated from the equation designed by Spinks and Woods (Equation

72)2

204

Equation 72

Where

F (Faradayrsquos constant) = 0965 x 109 A mol

-1

εFe(III) = Fe(III) molar extinction coefficient = 2174 M-1

cm-1

ρ = Fricke solution density = 1204 g mL-1

G = Critical Dose Value for Fe3+

= 148 molecules per 100 eV for x-rays

V = Volume of sample (mL) = 1

ODi = Optical density of irradiated solution

ODb = Optical density of non-irradiated control

The Spinks and Woods equation is specific to X-rays and must be adjusted so that it can

be applied to the use of γ-rays (Equation 73)

For γ-rays

εFe(III) = 2197 M-1

cm-1

G = 162 molecules per eV

Equation 73

Equation 74

Due to the design of the irradiator different positions in the machine receive

slightly different dose rates resulting in each sample receiving slightly different

amounts of radiation although the variation in dose is not significant and each sample

was calculated to receive an average of 114 Gy min-1

205


Co irradiator at DCF

Position Dose Rate (Gy

min-1

)

1 1084678

2 1171864

3 1183066

4 1103841

73 Solvent extraction and separation studies using amino acids and glutathione at

INL



A stock solution of Na5DTPA in H2O (1 M 100 mL) was made up from a 40

wv Na5DTPA solution in H2O by dilution (2517 g into 50 mL) A stock solution of L-

alanine in H2O (1 M 200 mL) was prepared from its crystalline form Additionally a

stock solution of HDEHP in n-dodecane (3224 g in 100 mL 1 M) was prepared This

was subsequently diluted with n-dodecane to prepare stock solutions of 02 04 06 and

08 M HDEHP in n-dodecane stock solutions as well

Stock solutions

1 M Na5DTPA in H2O

1 M L-Ala in H2O

10 08 06 04 02 M HDEHP in n-dodecane

7312 [Na5DTPA] dependence SX samples for amino acid studies

5 mL aqueous samples were prepared using the stock solutions above L-alanine

solution (25 mL) was added to a calculated volume of Na5DTPA solution to produce

samples with the desired DTPA concentration (006 007 008 009 01 02 03 04

05 M) when made up to 5 mL with water The pH of samples was adjusted individually

with concentrated HNO3 and NaOH to minimise change in volume using a Mettler

Toledo Seven Compact pHion Meter 02 M HDEHP in n-dodecane was used for the

solvent extraction All samples were repeated in triplicate

7313 [HDEHP] dependence SX samples for amino acid studies



samples with the desired DTPA concentration (01 02 03 04 05 M) when made up

206

to 5 mL with water The pH of samples was adjusted individually with concentrated

HNO3 and NaOH to minimise change in volume using a Mettler Toledo Seven

Compact pHion Meter 02 04 06 08 and 10 M HDEHP in n-dodecane was used for

the solvent extraction All samples were repeated in triplicate

7314 Other amino acid SX samples for amino acid studies

5 mL aqueous samples were prepared for L-His and L-Met buffered systems

The Na5DTPA stock solution (025 mL) was added to L-His (0388 g) and L-Met (0373

g) separately to make samples with concentrations of 005 M Na5DTPA and 05 M

amino acid when made up to 5 mL with water The powdered forms of the amino acids

were used due to their poor solubility The pH of samples was adjusted individually






wv Na5DTPA solution in H2O by dilution (2517 g into 50 mL) Additionally a stock

solution of HDEHP in n-dodecane (3224g in 100mL 1 M) was prepared This was

subsequently diluted with n-dodecane to prepare stock solutions of 02 04 06 and 08

M HDEHP in n-dodecane stock solutions as well

Stock solutions

1 M Na5DTPA in H2O


7316 [GSH] dependence SX samples without Na5DTPA

GSH (0768 g) was dissolved in water (5 mL) to make a 05 M solution The

powdered form of the peptide was used due to its poor solubility The pH of sample was

adjusted with concentrated HNO3 and NaOH to minimise change in volume using a

Mettler Toledo Seven Compact pHion Meter 02 M HDEHP in n-dodecane was used

for the solvent extraction All samples were repeated in triplicate

7317 [GSH] and pH dependence SX samples with Na5DTPA

5 mL aqueous samples were prepared for GSH buffered systems The Na5DTPA

stock solution (025 mL) was added to varying quantities of GSH to make samples with

207

concentrations of 005 M Na5DTPA and the desired concentration of GSH (01 02 03

04 05 M) when made up to 5 mL with water The pH of samples was adjusted

individually with concentrated HNO3 and NaOH to minimise change in volume using

a Mettler Toledo Seven Compact pHion Meter 02 M HDEHP in n-dodecane was used


7318 [Na5DTPA] dependence SX samples for GSH studies

5 mL aqueous samples were prepared for GSH buffered systems GSH (0768 g)

was added to a calculated volume of Na5DTPA solution to produce samples with

concentrations of 05 M GSH and the desired DTPA concentration (005 01 02 03

04 05 06 M) when made up to 5 mL with water The pH of samples was adjusted






was added to a calculated volume of Na5DTPA solution to produce samples with the

concentrations of 05 M GSH and the desired DTPA concentration (03 M and 04 M)

when made up to 5 mL with water The pH of samples was adjusted individually with

concentrated HNO3 and NaOH to minimise change in volume using a Mettler Toledo

Seven Compact pHion Meter 02 04 06 08 and 10 M HDEHP in n-dodecane was

used for the solvent extraction All samples were repeated in triplicate

732 Gamma counting

2 mL of each sample was transferred into a 4 mL sample vial in duplicate One

of the duplicate sets of samples was contacted with 2 mL n-dodecane to pre-equilibrate

the aqueous phase and the other duplicate set was contacted with the stock solution of

HDEHP in n-dodecane to pre-equilibrate the organic phase All of the samples were

then shaken using a VWR Multi-Tube Vortexer for 15 minutes Samples were then

placed in a Boeco S-8 Centrifuge for 5 minutes at 5400 rpm to separate the layers

The organic phase of the pre-equilibrated aqueous phase was discarded and the

aqueous phase of the pre-equilibrated organic phase was discarded 05 mL each

retained phase was then contacted in a 2 mL sample vial in triplicate and spiked with 10

microL 241

Am or 154

Eu stock solutions (1 kBq mL-1

) Samples were then shaken again using

208

a VWR Multi-Tube Vortexer for another 30 minutes before being placed in a Boeco S-

8 Centrifuge for 5 minutes at 5400 rpm to separate the layers

300 microL of each organic phase was transferred into counting tubes and 300 microL of

each aqueous phase was transferred into separate tubes Control tubes containing 300

microL HNO3 spiked with 10 microL 241

Am or 154


) were also

prepared γ counting was performed on the samples using a Packard Cobra II Gamma

Counter Results were averaged from each of the samples in triplicate

733 ICP-MS

Samples were made up as for SX samples with other amino acids for L-His and

(Section 7314) and for GSH (Section 7318) 2 mL of each sample was transferred

into a 4 mL sample vial 10 microL mixed Ln 110 stock solution (5 mgL-1

of each of La

Ce Pr Nd Sm Eu Gd Tb Dy Ho) was spiked into each sample and samples were

contacted with 2 mL HDEHP in n-dodecane (02 M) All of the samples were then

shaken using a VWR Multi-Tube Vortexer for 15 minutes Samples were then placed in

a Boeco S-8 Centrifuge for 5 minutes at 5400 rpm to separate the layers

The organic phase was discarded and 10 microL of the aqueous phase was

transferred into ICP-MS vials containing 10 mL 2 HNO3 in triplicate Control tubes

containing 10 mL 2 HNO3 spiked with 10 microL mixed Ln 110 stock solution were

also prepared ICP-MS was carried out to determine the concentration of each

lanthanide in the organic and aqueous phase Results were averaged from each of the

samples in triplicate

74 Luminescence studies and solvent extraction using glutathione at UoM



Stock solutions (10 mM (100 mM for Dy3+

) 10 mL) were made up for each

lanthanide (EuTbDySm) using the corresponding lanthanide nitrate salt

Ln(NO3)3xH2O in H2O or D2O as required A mixed lanthanide solution was also made

up to contain the same concentrations of each of the lanthanides above A stock solution

of Na5DTPA in H2OD2O (1 M 50 mL) was made up from a 40 wv Na5DTPA

solution in H2O by dilution (2517 g into 50 mL) Additionally a stock solution of

HDEHP in n-dodecane (3224 g in 100 mL 1 M) was prepared This was subsequently

diluted with n-dodecane to prepare stock solutions of 02 04 06 and 08 M HDEHP in

n-dodecane stock solutions as well All reagents were purchased from Sigma-Aldrich

209

Stock solutions

10 mM EuTbSm(NO3)3 in H2OD2O

100 mM Dy(NO3)3 in H2OD2O

Mixed Ln solution with 10 mM EuTbSm(NO3)3 in H2OD2O and 100 mM Dy(NO3)3




Samples were made up using the stock solutions above in the same way as for

the solvent extraction and separation studies carried out at INL (Sections 7312 to

7319) pD was calculated using Equation 71


5 mL aqueous samples were prepared using the stock solutions above GSH

(0768 g) was added to a calculated volume of Na5DTPA solution to produce samples

with the concentrations of 05 M GSH and the desired DTPA concentration (varied

according to the study) when made up to 5 mL with water The mixture was pre-






Meter pD was calculated using Equation 71 The aqueous phases were contacted with

5 mL HDEHP in n-dodecane (varied according to the study) The solutions were then

shaken again for 15 minutes left to settle and separated into the two phases for analysis

All samples were repeated in triplicate analagous to the solvent extraction samples

performed at INL


Radiolysis experiments on GSH buffered systems were carried out using the

60Co irradiator at DCF These irradiations were undertaken at a later date than the initial

amino acid radiolysis studies (Section 722) using a new calibrated sample holder with

known dose rates and so preparation and use of a Fricke solution was not necessary

Samples received an average of 7 kGy γ radiation

210



L-alanine methyl ester hydrochloride (0837 g 62 mmol) was dissolved in DMF

(15 mL) and added dropwise to DTPA dianhydride (107 g 3 mmol) in DMF (75 mL)

and 3 mL triethylamine (TEA) with stirring under nitrogen in an ice bath at 0 degC The

ice bath was removed after 2 hours and the reaction was left to stir at room temperature

for 48 hours The reaction was quenched with H2O (75 mL) and the solvent evaporated

to ~10 mL The resulting yellow oil was added dropwise to acetone (100 mL) with

stirring and the product precipitated The product was collected by sinter filtration

(porosity 3) under nitrogen as a crude white powder (yield 132 g 78) It was washed

with diethyl ether (3 x 20 mL) chloroform (3 x 20 mL) and diethyl ether again (3 x 20

mL) This was then dried under vacuum to give a white micro-crystalline product

(yield 1031 g 61 ) Multiple re-precipitations were performed to reduce the amount

of associated ammonium salts in the product Samples were dried under vacuum and

freeze-dried but water and solvent impurities continued to remain present

The synthesis was repeated using L-arginine methyl ester dihydrochloride (157 g 6

mmol) L-serine ethyl ester hydrochloride (102 g 6 mmol) and L-histidine methyl ester

(145 g 6 mmol)

Yields

DTPA-(AlaOMe)2 132 g 78 (MW 56356 gmol-1

)

DTPA-(ArgOMe)2 1331 g 60 (MW 73378 gmol-1

)

DTPA-(SerOEt)2 1053 g 56 (MW 62361 gmol-1

)

DTPA-(HisOMe)2 1730 g 83 (MW 69569 gmol-1

)

752 Characterisation of modified DTPA ligands by MALDI-MS

MALDI-MS was used to characterise the synthesised ligands Samples were

dissolved in methanol for analysis These analyses confirm that the ligands are the

desired ones as the protonated monomolecular ion [M+H]+ is visible in each case The

[M+Na]+ and [M+K]

+ ions can also be found in each spectrum The range begins at mz

= 200 so it is therefore not possible to verify the presence of triethylamine (M =

10119gmol) the amino acid starting material or any solvents using this technique The

spectra show a numerous peaks indicating that the ligands have decomposed during

analysis making interpretation difficult The spectrum for DTPA-(AlaOMe)2 can be

found in Appendix 6

211

DTPA-(AlaOMe)2 mz 565 (100) [M+H]+ 587 (37) [M+Na]

+ 603 (39) [M+K]

+

DTPA-(ArgOMe)2 mz 734 (100) [M+H]+ 756 (18) [M+Na]

+ 772 (9) [M+K]

+

DTPA-(SerOEt)2 mz 624 (100) [M+H]+ 646 (60) [M+Na]

+ 662 (15) [M+K]

+

DTPA-(HisOMe)2 mz 697 (100) [M+H]+ 719 (22) [M+Na]

+ 735 (10) [M+K]

+

753 Characterisation of modified DTPA ligands by NMR spectroscopy

NMR spectroscopy was performed on ligand samples in D2O (9992 atom D

Sigma Aldrich) at 400 MHz The 1H NMR spectra of DTPA-(AlaOMe)2 with suggested

peak assignments can be found in Appendix 7

The 1H NMR spectra are difficult to interpret and assign due to the number of

peaks and their proximity to each other There are also impurities observable in the

spectra 13

C NMR spectra were also recorded and were simpler to interpret due to the

DEPT 135 spectra and enabled the quaternary CH CH2 and CH3 carbons to be

distinguished 1H NMR assignments were made using HSQC relating each peak in a

1H

spectrum to its corresponding carbon Solvent impurities were determined from known

solvent shifts (DMF acetone ethanol chloroform andor diethyl ether)3 DMF is the

most prevalent impurity due to it being the most difficult solvent to remove Some

starting material from amino acid esters can also be observed in small quantities

Triethylammonium chloride is also present in a small amount (11 ppm and 30 pmm)


1H NMR Shifts (400 mHz D2O)

DTPA-(AlaOMe)2 δ ppm 125 (d 3JHH =734 Hz 6 H H8) 311 (t

3JHH =100 Hz 4 H

H5) 323 (t 3JHH =569 Hz 4 H H4) 348 - 355 (m 2 H H6 and H7) 362 - 369 (m

4 H H2) 375 - 387 (m 4 H H3) 418 - 425 (m 2 H H1)

DTPA-(ArgOMe)2 δ ppm 154 (dq 2JHH =1449 Hz

3JHH 730 Hz 4 H H9) 169 - 189

(m 4 H H8) 302 - 317 (m 4 H H10 ) 325 (s 8 H H4 and H5) 362 (s 4 H H2)

365 (s 6 H H7) 368 (s 2 H H6) 375 - 384 (m 4 H H3) 436 - 444 (m 2 H H1)

DTPA-(SerOEt)2 δ ppm 117 (t 3JHH =706 Hz 6 H H7) 327 (s 8 H H4 and H5)

364 - 372 (m 6 H H2 and H6) 378 - 393 (m 9 H) H3 and H9) 414 (q 3JHH =706

Hz 4 H H8) 452 (dd 3JHH =479 378 Hz 2 H H1)

DTPA-(HisOMe)2 δ ppm 297 - 323 (m 12 H H4 H5 and H8) 331 (s 4 H H2) 349

(s 4 H H3) 358 (s 6 H H7) 362 (m 2 H H6) 370 - 375 (m 1 H H3) 464 - 466

(m 2 H H1) 714 (s 2 H H9) 843 (s 2 H H10)

212




213


7532 13

C NMR Spectroscopy

13CNMR Shifts (400 mHz D2O)

DTPA-(AlaOMe)2 δ ppm 158 (CH3 C12) 485 (CH C1) 511 (CH2 C5) 514 (CH2

C4) 529 (CH3 C7) 543 (CH2 C6) 563 (CH2 C2) 564 (CH2 C3) 1686 (q-C C9)

1718 (q-C C11) 1721 (q-C C10) 1746 (q-C C8)

DTPA-(ArgOMe)2 δ ppm 243 (CH2 C13) 275 (CH2 C12) 404 (CH2 C14) 512

(CH2 C5) 518 (CH2 C4) 523 (CH C1) 530 (CH3 C7) 548 (CH2 C6) 564 (CH2

C2) 568 (CH2 C3) 1567 (q-C C15) 1698 (q-C C9) 1716 (q-C C11) 1728 (q-C

C10) 1735 (q-C C8)

DTPA-(SerOEt)2 δ ppm 132 (CH3 C8) 512 (CH2 C5) 514 (CH2 C4) 545 (CH2

C6) 549 (CH C1) 563 (CH2 C2) 565 (CH2 C3) 607 (CH2 C13) 628 (CH2 C7)

1693 (q-C C9) 1712 (q-C C10) 1717 (q-c C11) 1723 (CH3 C8)

DTPA-(HisOMe)2 δ ppm 257 (CH2 C12) 505 (CH2 C5) 517 (CH C1) 525 (CH2

C4) 531 (CH3 C7) 551 (CH2 C6) 568 (CH2 C2) 572 (CH2 C3) 1170 (CH C14)

1286 (q-C C13) 1333 (CH C15) 1711 (q-C C9) 1714 (q-C C11) 1716 (q-C

C10) 1746 (q-C C8)

214

Figure 75 13


Figure 76 13


Figure 77 13


215

Figure 78 13


754 Characterisation of modified DTPA ligands by elemental analysis

Elemental analysis was also performed on the ligands for characterisation Since

the ligands do contain impurities despite several purification steps the elemental

analysis is not quite as predicted for pure samples Chlorine was found to also be

present from residual triethylammonium chloride as identified by NMR spectroscopy in

addition to residual solvents despite prolonged drying under vacuum

Table 72 Elemental analysis results for modified DTPA ligands P = predicted

proportion present () A = actual proportion present ()

C () H () N () Cl () Na ()

Ligand P A P A P A P A P A

DTPA-(AlaOMe)2

4689 4224 662 685 1243 1146 0 475 0 0

DTPA-(ArgOMe)2

4583 3896 701 637 2100 1643 0 1427 0 0

DTPA-(SerOEt)2

4622 4300 663 755 1123 1041 0 240 0 0

DTPA-(HisOMe)2

4834 3985 594 668 1812 1458 0 595 0 0

216

755 Luminescence studies with modified DTPA ligands


A stock solution (10 mM 10 mL) was made up for Eu(NO3)3xH2O in H2O or

D2O as required Additionally a stock solution of HDEHP in n-dodecane (1935 g in

100 mL 06 M) was prepared All reagents were purchased from Sigma-Aldrich

Stock solutions




2 mL samples were prepared for aqueous phases The Eu(NO3)3 stock solution

(02 mL) was added calculated quantities of each ligand to make samples with

concentrations of 1 mM Eu(NO3)3 and 005 M ligand when made up to 2 mL with H2O

or D2O The pH of samples was adjusted individually with concentrated HNO3 and


Meter pD was calculated using Equation 71


Aqueous samples were prepared as above (Section 7413) Due to the small

quantities of ligand available pre-equilibration was not possible as the same samples

used for aqueous phase studies were subsequently used for extraction studies The

aqueous phases were contacted with HDEHP in n-dodecane (2 mL 06 M) The

solutions were then shaken using a Scientific Industries Vortex Genie 2 Mixer and

Shaker for 15 minutes left to settle and separated into the two phases for analysis


Radiolysis experiments on modified DTPA ligand systems were carried out

using the 60

Co irradiator at DCF These irradiations were undertaken at the same time as

the GSH irradiations at a later date than the initial amino acid radiolysis studies

(Section 722) using the new calibrated sample holder with known dose rates and so

preparation and use of a Fricke solution was not necessary Samples received an average

of 7 kGy γ radiation

217

76 Instruments


Co Irradiator

All irradiations at the Dalton Cumbrian Facility were carried out using a 60

Co

irradiator which can allow multiple dose rates as it comprises two individual source

rods Radiation is generated by the decay of 60

Co to 60

Ni causing emission of β-

particles and γ-rays

Samples (5 mL for amino acid and GSH systems 2 mL for modified DTPA

ligand systems) were transferred into glass vials with plastic screw tops and placed

inside the irradiator mounted on a pre-designed rig Multiple samples were able to be

irradiated at once due to the design of the sample holder (Figure 79)

Figure 79 60

Co Irradiator at DCF (left) sample holder (top right) and sample holder

inside the irradiator (bottom right)

762 Edinburgh Instrument FP920 Phosphorescence Lifetime Spectrometer

All luminescence studies were carried out using an Edinburgh Instrument FP920

Phosphorescence Lifetime Spectrometer Steady state emission and excitation spectra

were recorded in quartz cuvettes on an Edinburgh Instrument FP920 Phosphorescence

Lifetime Spectrometer equipped with a 5 watt microsecond pulsed xenon flashlamp

(with single 300 mm focal length excitation and emission monochromators in Czerny

Turner configuration) and a red sensitive photomultiplier in peltier (air cooled) housing

(Hamamatsu R928P) Lifetime data were recorded following excitation with the

flashlamp and using time correlated single photon counting (PCS900 plug-in PC card

for fast photon counting) Lifetimes were obtained by tail fit on the data obtained

218


ions


Activity in separation samples prepared at the INL was measured using a Cobra

II Gamma Counter an automated gamma counter Background samples were counted in

addition in order allow correction for background radiation levels Samples run on

automated protocols run until the counting error is within 1 or the sample has run for

20 minutes



NMR measurements were carried out using a Bruker UltrashieldTM

400

spectrometer of operating frequency 400 MHz (1H) and 162 MHz (

13C) with a variable

temperature unit set at 295 K unless otherwise stated The instrument was controlled

remotely using Bruker Topspin 21 software

Ln3+

Emission (nm) Excitation (nm)

Eu 617 395

Tb 545 379

Sm 600 403

Dy 575 352

219

1 CB Şenvar Chemical Dosimetry of Gamma Rays Neutrons and Accelerated

Electrons University of Ankara 1959 1-28

2 JWT Spinks and RJ Woods An Introduction to Radiation Chemistry Wiley-

Interscience Canada 3rd edn 1990

3 HE Gottlieb V Kotlyar and A Nudelman J Org Chem 1997 62 7512-7515

220

APPENDICES

APPENDIX 1 - Emission spectra for [GSH] pH dependence studies with DTPA in H2O

Figure A Emission spectra of Eu3+

in H2O at pH 2 with 005 M Na5DTPA over a GSH

concentration range of 01 ndash 05 M following excitation at 397 nm

Figure B Emission spectra of Eu3+



00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

221

Figure C Emission spectra of Eu3+



00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

222

APPENDIX 2 - SFLnAm for varying GSH concentration over a pH range of 2-4 with


Figure D SFLnAm for varying GSH concentration at pH 2 with 005 M Na5DTPA after


Figure E SFLnAm for varying GSH concentration at pH 3 with 005 M Na5DTPA after


0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

0

50

100

150

200

250

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

223

APPENDIX 3 - Natural pH values for modified DTPA ligands (005 M) with Eu(NO3)3

(1 mM)

Table F Natural pH values for modified DTPA ligands (005 M) with Eu(NO3)3 (1

mM)

Ligand Natural pH with Eu(NO3)3

DTPA-(AlaOMe)2 243

DTPA-(ArgOMe)2 238

DTPA-(SerOEt)2 240

DTPA-(HisOMe)2 286

224

APPENDIX 4 - Emission spectra for Eu(NO3)3 with modified DTPA ligands in H2O

Figure G Emission spectra for Eu(NO3)3 with modified DTPA ligands in H2O at pH 2

Figure H Emission spectra for Eu(NO3)3 with modified DTPA ligands in H2O at pH 3

0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

0

2

4

6

8

10

12

14

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

225

Figure I Emission spectra for Eu(NO3)3 with modified DTPA ligands in H2O at pH 4

0

1

2

3

4

5

6

7

8

9

10

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

226

APPENDIX 5 - Emission spectra for radiolysis studies on Eu(NO3)3 in H2O with

DTPA-di(amino acid) ligands

Figure J Emission spectra for Eu(NO3)3 in H2O with DTPA-di(amino acid) ligands

(005 M) at pH 2 after irradiation with 7 kGy γ-radiation

Figure K Emission spectra for Eu(NO3)3 in H2O with DTPA-di(amino acid) ligands


00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

tem

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

227

Figure L Emission spectra for Eu(NO3)3 in H2O with DTPA-di(amino acid) ligands


00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

228

APPENDIX 6 - MALDI-MS spectrum for DTPA-(AlaOMe)2

[M+H]+

[M+Na]+ [M+K]

+

229

AP

PE

ND

IX 7

- 1H N

MR

spectru

m fo

r DT

PA

-(AlaO

Me)

2

230

GSH1ESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alize

d In

tensi

ty

Water

44

944

844

6

38

9

37

6 37

437

2 28

628

628

528

4

24

924

8 24

724

624

524

4

21

1 20

920

720

5

AP

PE

ND

IX 8

- 1H N

MR

spectru

m fo

r GS

H

231

EUGSHESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alized Inte

nsity

Water

45

044

844

7

41

8

38

037

837

7

37

136

9

30

230

1

28

7 28

628

4

24

9 24

724

624

423

323

1

21

020

820

720

5

AP

PE

ND

IX 8

a - 1H N

MR

spectru

m fo

r Eu(N

O3 )

3 + G

SH

232

2

List of Tables

List of Figures

Abstract

Declaration

Copyright Statement

Acknowledgements

List of Symbols amp Units

List of Abbreviations amp Acronyms

Amino Acid Abbreviations

1 Introduction


111 Background

112 Sources of the Actinides and Lanthanides





117 Co-ordination Chemistry of the Lanthanides and

Actinides in Solution

1171 Hydrolysis









1224 Sensitised Luminescence and The Antennae

Effect


1226 Quenching


10

14

24

25

26

27

29

31

34

35

35

35

35

36

37

39

40

40

41

42

42

43

43

43

43

44

45

46

47

48

48

3


13 Nuclear Theory

131 Nuclear Power




1341 PUREX

1342 TRUEX

1343 DIAMEX

1344 SANEX

1345 iSANEX

1346 GANEX

1347 TRPO

1348 LUCA

1349 EXAm

137 TALSPEAK

1371 The Process



References






Complexes







50

51

51

52

53

55

55

57

59

60

62

63

65

67

68

69

69

74

75

77

81

81

82

83

84

84

86

88

88

89

4


and Ln-DTPA

Complexes


and Ln-DTPA

Complexes


and Ln-DTPA

Complexes


and [M(DTPA)]2-





Na5DTPA


Na5DTPA


Na5DTPA





References


Buffers












90

90

92

93

93

95

95

96

98

99

100

100

102

105

106

108

108

108

108

110

111

111

113

114

116

118

119

5




References


System





Na5DTPA


















441 Dy3+




Systems at pH 4



119

120

121

123

124

127

127

127

127

132

133

136

137

137

139

140

140

143

145

145

148

149

151

151

153

154

155

156

157

157

160

6




References



51 Ligand Synthesis











Work

References



62 Future Work

References





amp An3+

with amino acids in

TALSPEAK systems





163

166

170

173

174

175

176

176

179

183

183

184

185

186

187

190

191

192

192

198

200

201

201

201

201

201

201

202

202

7









amino acid studies


amino acid studies


acid studies



Na5DTPA


with Na5DTPA


GSH studies


amino acid studies

732 Gamma counting

733 ICP-MS


glutathione at UoM









MALDI-MS

203

203

203

205

205

205

205

205

206

206

206

206

207

207

207

208

208

208

208

209

209

210

210

210

210

8


NMR spectroscopy


7532 13

C NMR Spectroscopy


elemental analysis


ligands





76 Instruments


Co Irradiator






References

Appendices







(005 M) with Eu(NO3)3 (1 mM)





ligands


211

211

213

215

216

216

216

216

216

217

217

217

218

218

219

220

220

222

223

224

226

228

9





229

230

231

10

LIST OF TABLES








Reactors (LWR)


with amino

acidslactate




Am3+





[Eu(DTPA)]2-







system







values

Table 41 Eu3+

Am3+



11

Table 42 Eu3+

Am3+



Table 43 Eu3+

Am3+



pH 4

Table 44 Eu3+

Am3+



pH 4


with GSH at

pHD 4















in the




in the






γ-radiation

12








in the






and Tb3+

samples at pH 4




and Tb3+




HDEHP in dodecane












kGy γ-radiation



kGy γ-radiation

13


after Eu3+





phases after Eu3+





Co

irradiator at DCF



present ()


ions

14

LIST OF FIGURES


phosphorescence


Ln3+

complexes






U into 92

Kr and

141

Ba
























15













of MA3+

and Ln3+








pD = 36


a) pD 7 [DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]



in D2O

at pD 36


2- in 41 vv



and [Cm(DTPA)]2-

in




concentration






16



2- (10 mM) with L-



in D2O at pD 3 with



in





395 nm at 298 K



395 nm


in H2O with and


nm




and Am3+

in the presence of











system


Y3+


mM LnY3+





17






pH 2

Figure 37 Eu3+

Am3+



Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



Figure 310 Eu3+

Am3+




-Ho3+

and Am3+

with 05 M L-



acid (bottom)




Figure 44 Eu3+

Am3+




Figure 45 Eu3+

Am3+




Figure 46 Eu3+

Am3+



tests




18




Figure 410 Eu3+

and Am3+




and Eu3+


repeat tests

Figure 411 Eu3+

and Am3+



for Eu3+


Am3+


Figure 412 Eu3+

and Am3+




and Eu3+


from 3 repeat tests






at 397 nm



at 397 nm


Eu3+











19






extraction




extraction










Eu3+



nm


extraction





extraction







397 nm


Eu3+



of 01-06 M

20












10

mM Dy3+


for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

21




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)









Figure 442 1H


Cys (bottom)









extraction






nm




nm

22




nm





Eu3+





Am3+




Am3+




Am3+






kerosene







kerosene






Figure 75 13


Figure 76 13


23

Figure 77 13


Figure 78 13


Figure 79 60



24

ABSTRACT



PhD


Separations

2015









) components




allowing Ln3+





















Eu3+

Am3+










Eu3+

Am3+




Am3+



processes

25

DECLARATION




26

COPYRIGHT STATEMENT
























27

ACKNOWLEDGEMENTS





new experience





Adam Swinburne



all of your help





















28




work














29


gt greater than

˂ less than


percent


α alpha

β beta

γ gamma

δ chemical shift

Δ change in


λ wavelength

microL microlitres

micros microseconds

ρ density

τ lifetime

ν frequency

ν= energy level

wavenumber

Aring angstroms





au arbitrary units


hydration sphere

Bq Becquerel

cm centimetres



E energy

F Faradays constant

30

g grams


Gy Gray

h Plancks constant

Hz Hertz

J Joules


K Kelvin

kBq kiloBecquerel

kg kilograms

kGy kiloGray

kJ kiloJoules

L litres


M molar (moldm-3

)

mg milligrams

MHz megaHertz

min minute(s)

mL millilitres

mm millimetres

mM millimolar

mol moles

mmol millimoles

ms milliseconds

ng nanograms

nm nanometres

ns nanoseconds




s seconds

t time


31


An actinides

aq aqueous





Alternatives


mass spectrometry




















EC electron capture




32





FP fission products


GSH glutathione






I ionic strength





IR infra-red





Lac lactate



Ln lanthanides



M metal

MA minor actinides


spectrometry

MOX mixed oxide



33

nIR near-infra-red




org organic













TEA triethylamine













UV ultra-violet




34



Alanine Ala

Arginine Arg

Asparagine Asn

Aspartic acid Asp

Cysteine Cys

Glutamic Acid Glu

Glutamine Gln

Glycine Gly

Histidine His

Isoleucine Ile

Leucine Leu

Lysine Lys

Methionine Met

Phenylalanine Phe

Proline Pro

Serine Ser

Threonine Thr

Tryptophan Trp

Tyrosine Tyr

Valine Val

35

1 INTRODUCTION


111 Background










the early 20th

















commercially5




36












238U (n γ)

239U rarr

239Np rarr

239Pu (n γ)

240Pu (n γ)

241Pu rarr

241Am (n γ)

242mAm rarr

242Cm



processes6




ions can be














ions relatively

readily

β- β

- β

- β

-


37



Configuration

(Metal)

Electron

Configuration

(Ln3+

)

3rd

Ionisation

Energy

(kJmol-1

)

4th

Ionisation

Energy

(kJmol-1

)


2 [Xe] 1850 4819

Ce Cerium [Xe]4f15d

16s

2 [Xe]4f

1 1949 3547


2 [Xe]4f

2 2086 3761


2 [Xe]4f

3 2130 3899


2 [Xe]4f

4 2150 3970


2 [Xe]4f

5 2260 3990


2 [Xe]4f

6 2404 4110


16s

2 [Xe]4f

7 1990 4250


2 [Xe]4f

8 2114 3839


6s2 [Xe]4f

9 2200 4001

Ho Holmium [Xe]4f11

6s2 [Xe]4f

10 2204 4100

Er Erbium [Xe]4f12

6s2 [Xe]4f

11 2194 4115

Tm Thulium [Xe]4f13

6s2 [Xe]4f

12 2285 4119


6s2 [Xe]4f

13 2415 4220


5d16s

2 [Xe]4f

14 2022 4360












to

An3+

and An3+

to An2+


38


An4+





subshell of Cm3+





Config

(Metal)

Electron

Config

(An2+

)

Electron

Config

(An3+

)

Electron

Config

(An4+

)


2 NA [Rn]6d

1 [Rn]


17s

2 NA [Rn]5f

2 [Rn]5f

1

U Uranium [Rn]5f36d

17s

2 NA [Rn]5f

3 [Rn]5f

2


17s

2 NA

[Rn]5f

4 [Rn]5f

3


2 NA [Rn]5f

5 [Rn]5f

4


2 [Rn]5f

7 [Rn]5f

6 [Rn]5f

5

Cm Curium [Rn]5f76d

17s

2 NA [Rn]5f

7 [Rn]5f

6


2 NA [Rn]5f

8 [Rn]5f

7


7s2 [Rn]5f

10 [Rn]5f

9 [Rn]5f

8


7s2 [Rn]5f

11 [Rn]5f

10 [Rn]5f

9

Fm Fermium [Rn]5f12

7s2 [Rn]5f

12 [Rn]5f

11 [Rn]5f

10


7s2 [Rn]5f

13 [Rn]5f

12 [Rn]5f

11


7s2 [Rn]5f

14 [Rn]5f

13 NA


6d17s

2 NA [Rn]5f

14 NA

39



unknown8







Equation 11





Equation 12






Equation 13

7 NpO23+

PuO23+

AmO65-

6 UO22+

NpO22+

PuO22+

AmO22

+5 PaO2

+UO2

+NpO2

+PuO2

+AmO2

+

4 Th4+

Pa4+

U4+

Np4+

Pu4+

Am4+

Cm4+

Bk4+

Cf4+

3 Ac3+

Th3+

Pa3+

U3+

Np3+

Pu3+

Am3+

Cm3+

Bk3+

Cf3+

Es3+

Fm3+

Md3+

No3+

Lr3+

2 Am2+

Cf2+

Es2+

Fm2+

Md2+

No2+



40

































ions allows them

41


solution






the lanthanides












and the An3+




ion The Am7+


conditions



lanthanides

1171 Hydrolysis



and An3+






+ H3O+




AnO2+ lt An

3+ lt AnO2

2+ lt An

4+

42


position of AnO22+









ions having a






aqueous solution12









+ EDTA4-









43








The



Equation 16






Equation 17

Equation 18













44














does not



luminescent

45




spectrum




Pr3+

Sm3+

Nd3+

Eu3+

Ho3+

Tb3+

Er3+

Dy3+

Yb3+

Tm3+

Gd3+

(UV)

Ce3+

(UV)










and Th4+


has a full 4f


performed on Fm3+

Md3+

or No2+



Am3+

and Cm3+




46




spectrum



of the spectrum

NpO22+

Pa4+

(UV) Pa4+

Pa4+

Pa4+

Pa4+

Am3+

U4+

(UV) U4+

Es3+

UO2+

UO22+

UO22+

UO22+

UO22+

Am3+

Am3+

Am3+

Am3+

Cm3+

Bk3+

Cf3+
























47





complexes 1S



ion 19







(2S+1)LJ










48

1226 Quenching












) thermal




Tb3+



is very high

(20500 cm-1


Eu3+





Ho3+

Er3+

Tm3+

Yb3+

Dy3+

and Sm3+

with


has the









chromophores

49


3H4

4I132

4I112

3H4

3H5

3H6

3H6

3H5

3H4

0

20000

4I92

4I112

4I132

4I152

4F32

2H92

4S32

4F92

2H112

4G52

4G72

4G92

(2D2P)32

4G1125D4

7F07F17F27F37F4

7F5

7F67F0

7F1

7F2

7F3

7F4

7F5

7F6

5D0

5D1

5D2

2F52

2F72

10000

6H52

6H72

6H92

6H112

6H132

4F32

4G52

4F32

4F12

4F52

4F72

4G72

4F92

4F112

3F2

3F4

3P0

3P1

3F3

1I6

1G4

4I92

4F92

4S32

4F72

3F4

3F3

3F2

1G4

E

cm

-1

=0

=1

=2

=3

=4

=5

=0

=1

=2

=3

=4

=5

=6

=7

2H112

1D2







Figure 14

50













Equation 19

Equation 110





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+


51


and A = 42 for Tb3+




for Eu3+


for Tb3+

242526

13 Nuclear Theory

131 Nuclear Power








15


U into 92

Kr and 141

Ba27






52







(~2 kJ mol-1


C or 2H)










of 235

U238























53







produced




The amount of waste







54











Constituent of SNF

U 956


Pu 09

Cs amp Sr (FP) 03

I amp Tc (FP) 01


MA 01










However the




ions with ligands35


and

Cm3+

from Ln3+

55











the species36




Equation 111

Equation 112



1341 PUREX







Equation 113 UO22+


Equation 114 PuO22+


56


corresponding Pu4+


(Equation 115)





and 117)









4+ to Pu

3+ with



-


The Pu3+







The process






57


treatment40



1342 TRUEX




58
















59


1343 DIAMEX









The nitric



Oxalic acid is











60




1344 SANEX











61









bipyridine)




62


1345 i-SANEX





and Cm3+


and Ln3+

ions are









process50









been proposed51

63

1346 GANEX









over Eu3+

gt 1000







For the











bipyridine)

64




phenanthroline)

65


1347 TRPO

















66










67


1348 LUCA





from Cm3+

Cf3+

and Ln3+

after co-extraction






concentrations55




68


1349 EXAm





from Cm3+






and Ln3+

in




Cm3+

and TEDGA is





69

137 TALSPEAK






(Am3+

and Cm3+

) from

Ln3+

and yttrium (Y3+












problem

1371 The Process






for Nd3+







Without DTPA Eu3+

Am3+





70



TALSPEAK Process







separation




and

Ln3+



DTPA5-





phosphate)


HEH[ϕP] ((2-(2-


71




The Ln3+


of the DTPA5-



MA[DTPA]2-


is bound




4 After the Ln3+





rate as the DTPA5-


allowing them to be


dissociates The





separation If Ln3+

and Y3+




the raffinate



and Es3+

but it



72


DTPA to M3+


extraction of Ln3+
















1 2

73


and Ln3+


60



An3+






chemistry62

74



















75






in storage









practicality




Initial research in
















have been explored

76


















77











1966 1 6-10














2188







Chem Rev 2014 266-267 171-193




78











Great Britain 1999









2012



Compounds 2000 303-304 137-141



Cambridge UK 2011



130-134


3373-3376




79


Extr Ion Exch 1985 31 75-109





1997 47 57-67














29 190








7 349-357




377


2010 28 3 287-312

80








2892-2893





282 523-526


50 7937-7939

81






























radiotherapy7

82







of LnDTPA2-


to take place For

LnDTPA2-




complexes






- 2348 for CmDTPA2-






2219 - 2085 for CmDTPA2-






Cm3+




83

strength to DTPA5-

than Eu3+


CmDTPA2-

than EuDTPA2-

(-407 kJ mol-1

vs -336 kJ mol-1

) determined by


to DTPA5-

than Eu3+


CmDTPA2-



in D2O for Cm3+




was







to the ligand









extraction as the

MDTPA2-











LnHDTPA- species


84


to MA3+


octadentate





and EuDTPA2-




than Eu3+


Cm3+






to MHDTPA-


than Eu3+

so



3+ This data is








H2O)










85

EUDTPAESP

15 10 5 0 -5 -10 -15 -20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

152

8

99

196

6

88

4

53

7

42

536

033

528

7

15

8

-01

1

-16

1

-40

6

-57

3-6

33

-105

3

-126

8

-148

3

-170

2

-184

7


2- in D2O at 278 K at pD = 36

DTPA pH71resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

199100215418

DEUTERIUM OXIDE

Water

38

1

34

033

833

632

8

30

630

530

3

a

86

DTPA pH361resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

204206100421

Water

47

647

5

38

5

35

634

634

434

3

31

531

431

2

DTPA pH21resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

202199100406

Water

47

5 46

9

39

0

35

4

34

033

933

7

31

130

930

8


[DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]




5- (005






Eu3+




ligand to Eu3+

ion at pH 361617



to DTPA5-


b

c

87


solvent molecules



in D2O at pD 36


(aq) and the

[Eu(DTPA)]2-







Equation 21

Equation 22





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+



and A = 42 for Tb3+


0

2

4

6

8

10

12

14

16

18

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

[Eu(DTPA)]2-

Eu3+

5D0 rarr 7F0

5D0 rarr 7F1

5D0 rarr 7F2

5D0 rarr 7F3

5D0 rarr 7F4

88

0075x) ms-1


and A =

5 ms and B = 006 ms-1

for Tb3+



ion is










ions

than Ln3+



and Cm3+

complexation



and Cm3+








the 241







The Am3+



89


but in this ion




the second J




Indeed


[Am(DTPA)xH2O]2-


7F1 excited







243Cm

3+ (015 microM Cm

3+ in 32



Cm3+




8S72


3+(aq)


in Cm3+


due to more

210 K

265 K

300 K

365 K

90





and [Cm(DTPA)]2-



Similarly to Eu3+


ion is known to





Equation 23













ions27

to form

40

45

50

55

60

65

70

75

80

570 590 610 630

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

Cm3+(aq)

[Cm(DTPA)]2-

91

M3+


3+-lactate

complexes

Equation 24a-c

(a)

(b)

(c)









5D0 rarr



ion changes as a









92

mode to Ln3+





28



ion and the








over Am3+

DTPA is required to


from Ln3+


holdback reagent



and M(Lac)n3-n

Studies carried






ternary M3+








93







ions32





668


and [M(DTPA)]2-






(bottom right)



1H




94

New Eu Ala0011resp

55 50 45 40 35 30 25 20 15 10 05 0


0

005

010

015

Norm

alized Inte

nsity

310100

CH3

CH

Water

47

147

1

35

5

12

712

6


278 K

Ala1resp

55 50 45 40 35 30 25 20 15 10 05 0


0

01

02

03

04

05

06

07

08

09

10

Norm

alized Inte

nsity

336100

CH3

CH

Water

36

536

336

2

13

3


95







EuDTPA Ala1esp

15 10 5 0 -5 -10 -15 -20


0005

0010

0015

0020

0025

0030

0035

Norm

alized Inte

nsity

150

5 96

892

185

2

75

4

50

4

39

533

231

625

8

14

6

05

0

-13

1

-44

2

-63

3-6

86

-108

2

-127

6

-143

1

-169

0

-183

9



at 278 K
















96


region (Figure 214)













0

100

200

300

400

500

600

700

0

5

10

15

20

25

30

220 320 420 520 620

Ab

sorp

tio

n In

ten

sity

(au

) Th

ou

san

ds

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

TbDTPA exc 379 nm




97

















seen in Table 21

0

2

4

6

8

10

12

14

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+

Eu-Lactate

Eu-Gly

Eu-Ala

Eu-Ser

98








metal







0

5

10

15

20

25

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser


Eu3+

011 165 89


Eu Gly 016 183 60

Eu Ala 016 187 60

Eu Ser 019 147 48

99


to [Eu(DTPA)]2-








seen in Table 22


with amino



upon


the Eu3+












Eu DTPA 063 230 23





100







Cm3+

to DTPA5-


[Cm(DTPA)]2-









processes33









40

45

50

55

60

65

70

75

80

570 580 590 600 610 620 630 640

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

[Cm(DTPA)]2-

[Cm(DTPA)]2- + Ala

101











from Am3+









32 33 34 3517

18

19

20

21

Alanine (pH 30)

Lactate ion (pH 60)

Lactic acid (pH 10)

ToC k M

-1 s

-1Error

1046 59E7 49E6

306 849E7 421E6

305 832E7 419E6

402 102E8 816E6




R2 = 0990

ln (

kM

-1 s

-1)

103Temp (K)

102


and Am3+




Am3+



not defined



pH 2 5620 5519 5132 5103

pH 3 1595 1653 1589 1252


The [Eu(DTPA)]2-




103










0

50

100

150

200

250

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

0

20

40

60

80

100

120

140

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

104








[Eu(DTPA)]2-




systems before and


τ of aqueous

phase

before

irradiation

(ms)

τ of aqueous

phase

after

irradiation

(ms)

τ of

organic

phase

before

irradiation

(ms)

τ of

organic

phase

after

irradiation

(ms)

Eu DTPA 063 066 222 262


Eu DTPA Gly 065 064 247 249

Eu DTPA Ala 065 065 211 238

Eu DTPA Ser 065 062 260 251

τ of

aqueous

phase

before

irr [H2O]

(ms)

τ of

aqueous

phase

after

irr[H2O]

(ms)

τ of

aqueous

phase

before irr

[D2O] (ms)

τ of

aqueous

phase

after irr

[D2O] (ms)

q

before

irr

q after

irr

Eu DTPA 063 066 230 227 11 10

Eu DTPA

Lactate

063 063 216 210 10 10

Eu DTPA

Gly

065 064 203 208 10 10

Eu DTPA

Ala

065 065 209 211 10 10

Eu DTPA

Ser

065 062 208 206 10 10

105











and [Eu(DTPA)]2-






ion when



and Cm3+



amino acidslactate


was





or Cm3+


[Eu(DTPA)]2-





106



2788


6445





107 758-769


1999 42 15 2988ndash2992





1968 10 94

11 I Bayat KFK



2013 101 221









89





107










271273 719





14547-14556


313-334




97 9 497-502







108


ACID BUFFERS












MA3+
























3 A pH 1 system

109



comparison

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring



Y3+


1 M


110












086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring


system

111










Lactic

Acid

10 3 0009 380 140 mdash 91







ions including Ln3+

and An3+

Aziz et al67


and Am3+

at pH 36












ion with



112


















113








H7DTPA2+


3+ and Ln






Ln3+

ions is H3DTPA2-

At pH 3 a much







INL

114







115





over Am3+













phase

y = -09383x - 15277 Rsup2 = 09854

y = -11258x + 01381 Rsup2 = 09289

-10

-05

00

05

10

15

20

-125 -12 -115 -11 -105 -1 -095

log

DEu

Am

log [Na5DTPA]

Am Extraction

Eu Extraction

116

Figure 37 Eu3+

Am3+


M) at pH 2










less Am3+







y = -08451x - 14757 Rsup2 = 09936

y = -07958x + 03998 Rsup2 = 0998

-15

-10

-05

00

05

10

15

-11 -1 -09 -08 -07 -06 -05 -04 -03

log

DEu

Am

log [Na5DTPA]


117

Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



y = 13522x + 02972 Rsup2 = 09283

y = 09682x + 19794 Rsup2 = 09561

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

y = 14702x + 00193 Rsup2 = 09981

y = 11892x + 17129 Rsup2 = 09713

-10

-05

00

05

10

15

20

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

118

Figure 310 Eu3+

Am3+













[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10




y = 11522x - 00047 Rsup2 = 09867

y = 12575x + 18424 Rsup2 = 09976

-10

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

119


[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 012 053 121 126 203

03 010 027 050 077 102

04 008 036 051 077 102



















in Table 35

120













Buffer pH DAm

DEu

SF

Lactic Acid 3 0009 0819 91


2 018 1016 57


2 053 4463 84

3 007 660 99

121


-Ho3+

and Am3+


pH 2 and pH 3






higher pH




Ln3+

Am3+











001

01

1

10

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

His pH 2

His pH 3

Am pH 2

Am pH 3

122












other amino acids

123


2014 32 378-390















2010 28 3 287-312

124


SYSTEM






in an aqueous

phase allowing Ln3+







industrial process









42)

125


(bottom)


vitamin B9 (bottom)






126














Ln3+

separation












to 751

for Ho3+









127



and Eu3+



















and Am3+

Over a



temperature







128

Figure 44 Eu3+

Am3+



tests

Figure 45 Eu3+

Am3+



tests




over Am3+


-02

0

02

04

06

08

1

12

14

16

18

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

-1

-08

-06

-04

-02

0

02

04

06

08

1

12

14

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

129










Figure 46 Eu3+

Am3+









-15

-10

-05

00

05

10

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

130

Table 41 Eu3+

Am3+


Na5DTPA at pH 4













131














4 (right)10

132











Figure 410 Eu3+

and Am3+



and Eu3+

Results


y = 19018x2 - 23123x + 72258 Rsup2 = 09937

y = 0442x2 - 03543x + 00659 Rsup2 = 0781

00

00

01

01

02

-20

-10

00

10

20

30

40

50

60

70

-01 26E-15 01 02 03 04 05 06 D

Am

DEu

[Na5DTPA] (M)

Eu extraction

Am extraction

133

Table 42 Eu3+

Am3+































134

Figure 411 Eu3+

and Am3+






Table 43 Eu3+

Am3+















y = -30649x2 + 3243x + 15029 Rsup2 = 09467

y = 00013x + 00015 Rsup2 = 08028

0000

0002

0004

0006

0008

0010

0012

0014

00

05

10

15

20

25

30

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

135

Figure 412 Eu3+

and Am3+



and Eu3+


Table 44 Eu3+

Am3+

















these conditions

y = -01882x + 08847 Rsup2 = 08326

y = 17968x - 04007 Rsup2 = 09946

-0500

0000

0500

1000

1500

2000

00

01

02

03

04

05

06

07

08

09

10

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

136



















0

1

2

3

4

5

6

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+ in H2O

Eu with GSH

Eu with DTPA

137

























in each case (q)

00

01

02

03

04

05

06

07

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

138


















00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

139


with GSH at pHD 4


[GSH]

(M)


01 1487 428 17

02 785 353 16

03 829 440 11

04 1545 161 58

05 1016 168 52







extraction at



Eu3+






00

01

01

02

02

03

03

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


140


ion is extracted as


spectrum11












00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

141










00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

142



J=1J=2

[GSH] (M)

01 02 03 04 05 st dev t-test

pD 2 0335 0399 0379 0375 0361 0024 No sig diff

pD 3 0440 0433 0451 0439 0419 0012 No sig diff

pD 4 0438 0467 0413 0469 0454 0023 No sig diff

st dev 0060 0034 0036 0048 0047

















143




pH 2 01 1699 plusmn 7 607 plusmn 9 10

pH 2 02 1692 plusmn 10 619 plusmn 10 09

pH 2 03 1686 plusmn 9 629 plusmn 9 09

pH 2 04 1636 plusmn 12 607 plusmn 13 09

pH 2 05 1596 plusmn 11 629 plusmn 13 09

pH 3 01 1755 plusmn 14 626 plusmn 7 09

pH 3 02 1737 plusmn 13 626 plusmn 15 09

pH 3 03 1723 plusmn 5 626 plusmn 13 09

pH 3 04 1720 plusmn 14 635 plusmn 17 09

pH 3 05 1677 plusmn 9 641 plusmn 14 09

pH 4 01 1778 plusmn 14 593 plusmn 16 10

pH 4 02 1747 plusmn 13 640 plusmn 15 09

pH 4 03 1679 plusmn 15 669 plusmn 18 08

pH 4 04 1689 plusmn 14 623 plusmn 15 09

pH 4 05 1679 plusmn 13 652 plusmn 19 08



complex The




GSH with the Eu3+







144















00

05

10

15

20

25

30

35

40

45

50

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Aq

03 M GSH pH 4 Aq

05 M GSH pH 4 Aq

05 M GSH pH 3 Aq

05 M GSH pH 2 Aq

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Org

03 M GSH pH 4 Org

05 M GSH pH 4 Org

05 M GSH pH 3 Org

05 M GSH pH 2 Org

145





as the HDEHPDEHP



ions GSH is




varied

J=1J=2

[GSH] (M)


pD 4 0202 0276 0247 0037 No sig diff

pD 3 - - 0100 - -

pD 2 - - 0500 - -

st dev - - 0202

t-test - - Sig diff







146










0

5

10

15

20

25

30

35

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

0

2

4

6

8

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

147



J=1J=2

[Na5DTPA] (M)

005 01 02 03 04 05 06 stdev t-test

D2O 0437 0441 0431 0437 0428 0425 0403 0013

No sig

diff

H2O 0450 0440 0437 0449 0422 0424 0428 0011

No sig

diff


















with GSH

148



[Na5DTPA]

(M)


005 1679 plusmn 3 652 plusmn 2 08

01 1549 plusmn 4 659 plusmn 2 10

02 1348 plusmn 4 666 plusmn 3 09

03 1179 plusmn 4 665 plusmn 3 08

04 1076 plusmn 4 674 plusmn 4 07

05 978 plusmn 4 698 plusmn 4 05

06 916 plusmn 5 714 plusmn 5 03






extraction with



0

1

2

3

4

5

6

7

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

149








phase





J=1J=2 0552 0578 0502 0039 No sig

diff






and 426

150














J=1J=2 0472 0499 0455 0510 0025 No sig

diff

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Aq

06 M HDEHP Aq

08 M HDEHP Aq

10 M HDEHP Aq

151





The lowest Eu3+



concentrations Am3+








Facility using a 60



seen in Figure 427

00

00

00

01

01

01

01

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Org

06 M HDEHP Org

08 M HDEHP Org

10 M HDEHP Org

152











00

01

01

02

02

03

03

04

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

153




[Na5DTPA] (M)

01 02 03 04 05 06 st

dev

t-test

J=1J=2 0477 0481 0452 0401 0407 0411 0036

No sig

diff



kGy γ-radiation


01 648 plusmn 4 1895 plusmn 12 10

02 661 plusmn 6 1678 plusmn 10 09

03 670 plusmn 6 1536 plusmn 11 08

04 679 plusmn 5 1462 plusmn 9 07

05 701 plusmn 7 1328 plusmn 10 05

06 696 plusmn 6 1211 plusmn 8 03






154


extraction from


range of 01-06 M















J=1J=2 0505 0563 0551 0031 No sig diff



under a variety



0

1

2

3

4

5

6

7

8

9

10

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Hu

nd

red

s

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

155



Also like Eu3+



441 Dy3+







is relatively








6H152 and

7F92 rarr







00

02

04

06

08

10

12

14

16

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O

Dy DTPA

Dy GSH

7F92 rarr

6H152

7F92 rarr

6H132

156







352 nm









lanthanides







00

02

04

06

08

10

12

14

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O Aq

Dy DTPA Aq

Dy GSH Aq

Dy H2O Org

Dy DTPA Org

Dy GSH Org

157



excitation







Systems at pH 4

The Dy3+



Eu3+

Tb3+

and Dy3+




irradiation





data

00

01

02

03

04

05

06

07

08

09

10

550 560 570 580 590

Emis

sio

n In

ten

sity

(au

) x 1

00

00

Wavelength (nm)

pH 2 Aq

pH 3 Aq

pH 4 Aq

pH 4 (03 M DTPA) Aq

pH 2 Org

pH 3 Org

pH 4 Org


158


10 mM Dy3+

) in H2O


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10 mM Dy3+

) with


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

0

5

10

15

20

25

30

35

40

45

50

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

0

2

4

6

8

10

12

14

16

18

20

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

159


10 mM Dy3+

005 M


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)








complex can also be

seen for the Tb3+



or Dy3+




Ln3+


Ln3+

with

GSH



0

1

2

3

4

5

6

7

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

160





and Tb3+

as calculations of

q for Sm3+

and Dy3+




ion with




and Tb3+

samples at pH 4


Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

Ln3+


Ln3+

with

GSH











and Tb3+

are as



161


10 mM Dy3+

) with


397

nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


pH range of 2-4







and Tb3+

samples before



Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)




00

10

20

30

40

50

60

70

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

162





with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

163


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)







and Dy3+



and Eu3+





the Ln3+



Ln3+


MS






00

05

10

15

20

25

30

35

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

164







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

0

5

10

15

20

25

30

35

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

165

















166



pH

[GSH]

(M)

SF


2 01 234 171 148 107 136 158 216 222 237 234

2 02 244 176 145 103 134 146 215 229 239 244

2 03 263 183 145 105 137 165 243 244 281 289

2 04 239 170 151 111 145 168 218 237 259 265

2 05 278 197 164 117 162 189 257 269 300 314

3 01 1735 972 477 276 163 104 112 53 41 38

3 02 1953 841 433 256 320 266 290 130 89 77

3 03 1898 785 388 220 152 90 95 39 28 24

3 04 2046 812 412 243 196 121 126 53 38 34

3 05 2145 705 312 139 36 16 20 04 02 00

4 01 3777 141 12 - - - - - - -

4 02 5548 231 36 06 - - - - - -

4 03 2768 239 27 - - - - - - -

4 04 1620 150 21 01 - - - - - -

4 05 1589 286 48 11 - - - - - -







167

GSH0011resp

45 40 35 30 25 20 15 10


0

005

010

Norm

alized Inte

nsity

197201200100200099

c

d

gb

i

f

44

944

844

6

38

9

37

637

437

2

28

628

628

528

4

24

924

824

724

624

524

4

21

120

920

720

5


45 40 35 30 25 20 15 10


0

005

010

015

020

025

Norm

alized Inte

nsity

133151244272014101206498131111059100

m

c

d

n

g

q

b

l

i

p

f

47

0

44

7 44

544

442

942

841

641

541

140

940

940

738

137

737

537

3

36

736

6

29

929

728

428

328

1

26

7

24

6

24

424

324

223

823

022

822

6

20

720

520

419

6

19

519

419

319

1

a

b

168

Eu GSH0011resp

45 40 35 30 25 20 15 10


005

010

015

Norm

alized Inte

nsity

035183050206177050088216024026100

d

g

b

i

f

c

45

044

844

7

42

0 41

841

741

341

241

138

0 37

837

737

136

9 30

230

1

28

928

728

628

428

328

1

25

124

924

724

624

424

2 23

3 23

122

921

020

820

720

519

919

819

719

6

GSH DTPA0011resp

45 40 35 30 25 20 15 10


0

005

010

015

Norm

alized Inte

nsity

032158045179156092075366021025099

c

d

g

DTPA

DTPA

DTPA

b

DTPA

i

f

45

044

9 44

744

6

41

941

841

741

241

141

0

37

937

737

537

036

8

34

133

633

5

30

730

530

1

28

928

628

528

428

228

0

25

024

824

624

524

324

1 23

223

022

821

020

820

620

419

719

5

c

d

169

EuDTPA GSH0011resp

45 40 35 30 25 20 15 10


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

180181200200212103673021100

47

0

44

244

1

38

4

36

836

3

32

832

0 30

230

129

9 28

628

528

328

1

24

724

624

524

424

3

20

820

720

520

3




Figure 442 1H





e

170













422)









and Am3+

when used without

Na5DTPA





Eu3+

and Am3+





experiments






171


extraction























with pH







conditions






172





irradiation











Dy3+




decreasing as


for Tb3+

and Dy3+


and Eu3+













173

















Chem B 2012 116 46 13722-13730


Chem 2010 8 4915-4920



174











) ions


by HDEHP (di-



considered






the MA3+



over Ln3+

This is













INE

175





















Protected

Protected Protected

176













0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

177






Eu3+




centre as expected


complexes at pD 2-4

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

0

5

10

15

20

25

30

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

178

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pD 2 0359 0381 0404 0353 0023

No sig

diff

pD 3 0394 0425 0417 0381 0020

No sig

diff

pD 4 0391 0427 0432 0423 0019

No sig

diff

st dev 0019 0026 0014 0035

t-test No sig

diff

No sig

diff

No sig

diff

No sig

diff












179



excitation

















itself








180




at 397 nm


extraction from



0

0

0

0

0

1

1

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

0

10

20

30

40

50

60

70

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


181


extraction from




extraction from



0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


0

1

2

3

4

5

6

7

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

Ala-DTPA Org

Arg-DTPA Org

His-DTPA Org

Ser-DTPA Org

182























Eu3+


pH 2-4

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pH 2 0208 0207 0198 0208 0005 No sig diff

pH 3 0210 0213 0311 0347 0069 Sig diff

pH 4 0182 0210 0206 0205 0013 No sig diff

st dev 0016 0003 0063 0081


183












397 nm





0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

184



DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-


J=1J=2 0357 0395 0412 0362 0026 No sig

diff













extraction from



0

1

2

3

4

5

6

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


185












DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

J=1J=2 0241 0233 0198 0231 0019

No sig

diff





without irradiation

(micros)


irradiation









186



Am + 152

Eu (1 kBq mL-1






and Eu3+








and Eu3+

for these











Am3+

using DTPA-


187


Am3+

using DTPA-



Am3+

using DTPA-




Am3+





and Am3+

can be seen in


Am3+

(as

188

Nd3+









189







190






complex to Eu3+





over Am3+





with the ligands








between Ln3+

Am3+






Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30








191






192





and MA3+




allowing Ln3+












from Ln3+

23









Ln3+




Am3+

is achieved








organic phase

193


keeping Am3+

















lanthanides



and [Eu(DTPA)]2-






Eu3+




ion when



and Cm3+





or Cm3+




194







and the



operation








and Am3+

when used without

Na5DTPA






Eu3+

and Am3+




the pH is increased







Am3+


TALSPEAK process



195

































can occur Further




Eu3+

Tb3+

and Dy3+






196




and Dy3+

which are


and Eu3+



-Ho3+






acid systems



Eu3+

Am3+









MA3+







at pH 2 3 and 4











irradiation



between Ln3+

Am3+


197





Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30



















the use of amino







with lactate15


Cm3+

with DTPA16


with





however there are



198

62 Future Work
















199




















and Cm3+














ratio of Am3+





200




10 245-279



523-526






2014 32 378-390





47 8856



2012 65 16 2862-2876











amino-acidshtm 2015




201
























were returned


amp An3+









202






Stock solutions




0625 M L-Phe in D2O







1 M amino








Equation 71









203







such as from a 60




H2O rarr H + OH

OH + Fe2+

rarr Fe3+

+ HO-

H + O2 rarr HO2

H+ + Fe

2+ + HO2 rarr Fe

3+ + H2O2

H2O2 + Fe2+

rarr Fe(OH)2+

+ OH

HO2 + Fe3+

rarr Fe2+

+ O2 + H+


ions to Fe3+

The amount

of Fe3+





out using the 60










72)2

204

Equation 72

Where


-1


cm-1









For γ-rays

εFe(III) = 2197 M-1

cm-1


Equation 73

Equation 74





205




min-1

)

1 1084678

2 1171864

3 1183066

4 1103841


INL









Stock solutions

1 M Na5DTPA in H2O

1 M L-Ala in H2O














206




















Stock solutions

1 M Na5DTPA in H2O











207






















732 Gamma counting










microL 241

Am or 154



208






Am or 154


) were also



733 ICP-MS




of each of La
























209

Stock solutions
























performed at INL







210


















(145 g 6 mmol)

Yields


)


)


)


)





[M+Na]+ and [M+K]






found in Appendix 6

211


+ 603 (39) [M+K]

+


+ 772 (9) [M+K]

+


+ 662 (15) [M+K]

+


+ 735 (10) [M+K]

+







spectra 13




1H









3JHH =100 Hz 4 H


4 H H2) 375 - 387 (m 4 H H3) 418 - 425 (m 2 H H1)


3JHH 730 Hz 4 H H9) 169 - 189


365 (s 6 H H7) 368 (s 2 H H6) 375 - 384 (m 4 H H3) 436 - 444 (m 2 H H1)



Hz 4 H H8) 452 (dd 3JHH =479 378 Hz 2 H H1)


(s 4 H H3) 358 (s 6 H H7) 362 (m 2 H H6) 370 - 375 (m 1 H H3) 464 - 466

(m 2 H H1) 714 (s 2 H H9) 843 (s 2 H H10)

212




213


7532 13

C NMR Spectroscopy




1718 (q-C C11) 1721 (q-C C10) 1746 (q-C C8)




C10) 1735 (q-C C8)



1693 (q-C C9) 1712 (q-C C10) 1717 (q-c C11) 1723 (CH3 C8)



1286 (q-C C13) 1333 (CH C15) 1711 (q-C C9) 1714 (q-C C11) 1716 (q-C

C10) 1746 (q-C C8)

214

Figure 75 13


Figure 76 13


Figure 77 13


215

Figure 78 13










C () H () N () Cl () Na ()


DTPA-(AlaOMe)2

4689 4224 662 685 1243 1146 0 475 0 0

DTPA-(ArgOMe)2

4583 3896 701 637 2100 1643 0 1427 0 0

DTPA-(SerOEt)2

4622 4300 663 755 1123 1041 0 240 0 0

DTPA-(HisOMe)2

4834 3985 594 668 1812 1458 0 595 0 0

216






Stock solutions



















using the 60






217

76 Instruments


Co Irradiator


Co



Co to 60







Figure 79 60













218


ions






20 minutes




400





Ln3+


Eu 617 395

Tb 545 379

Sm 600 403

Dy 575 352

219






220

APPENDICES








00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

221




00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

222







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

0

50

100

150

200

250

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

223


(1 mM)


mM)


DTPA-(AlaOMe)2 243

DTPA-(ArgOMe)2 238

DTPA-(SerOEt)2 240

DTPA-(HisOMe)2 286

224




0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

0

2

4

6

8

10

12

14

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

225


0

1

2

3

4

5

6

7

8

9

10

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

226







00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

tem

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

227



00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

228


[M+H]+

[M+Na]+ [M+K]

+

229

AP

PE

ND

IX 7

- 1H N

MR

spectru

m fo

r DT

PA

-(AlaO

Me)

2

230

GSH1ESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alize

d In

tensi

ty

Water

44

944

844

6

38

9

37

6 37

437

2 28

628

628

528

4

24

924

8 24

724

624

524

4

21

1 20

920

720

5

AP

PE

ND

IX 8

- 1H N

MR

spectru

m fo

r GS

H

231

EUGSHESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alized Inte

nsity

Water

45

044

844

7

41

8

38

037

837

7

37

136

9

30

230

1

28

7 28

628

4

24

9 24

724

624

423

323

1

21

020

820

720

5

AP

PE

ND

IX 8

a - 1H N

MR

spectru

m fo

r Eu(N

O3 )

3 + G

SH

232

3


13 Nuclear Theory

131 Nuclear Power




1341 PUREX

1342 TRUEX

1343 DIAMEX

1344 SANEX

1345 iSANEX

1346 GANEX

1347 TRPO

1348 LUCA

1349 EXAm

137 TALSPEAK

1371 The Process



References






Complexes







50

51

51

52

53

55

55

57

59

60

62

63

65

67

68

69

69

74

75

77

81

81

82

83

84

84

86

88

88

89

4


and Ln-DTPA

Complexes


and Ln-DTPA

Complexes


and Ln-DTPA

Complexes


and [M(DTPA)]2-





Na5DTPA


Na5DTPA


Na5DTPA





References


Buffers












90

90

92

93

93

95

95

96

98

99

100

100

102

105

106

108

108

108

108

110

111

111

113

114

116

118

119

5




References


System





Na5DTPA


















441 Dy3+




Systems at pH 4



119

120

121

123

124

127

127

127

127

132

133

136

137

137

139

140

140

143

145

145

148

149

151

151

153

154

155

156

157

157

160

6




References



51 Ligand Synthesis











Work

References



62 Future Work

References





amp An3+

with amino acids in

TALSPEAK systems





163

166

170

173

174

175

176

176

179

183

183

184

185

186

187

190

191

192

192

198

200

201

201

201

201

201

201

202

202

7









amino acid studies


amino acid studies


acid studies



Na5DTPA


with Na5DTPA


GSH studies


amino acid studies

732 Gamma counting

733 ICP-MS


glutathione at UoM









MALDI-MS

203

203

203

205

205

205

205

205

206

206

206

206

207

207

207

208

208

208

208

209

209

210

210

210

210

8


NMR spectroscopy


7532 13

C NMR Spectroscopy


elemental analysis


ligands





76 Instruments


Co Irradiator






References

Appendices







(005 M) with Eu(NO3)3 (1 mM)





ligands


211

211

213

215

216

216

216

216

216

217

217

217

218

218

219

220

220

222

223

224

226

228

9





229

230

231

10

LIST OF TABLES








Reactors (LWR)


with amino

acidslactate




Am3+





[Eu(DTPA)]2-







system







values

Table 41 Eu3+

Am3+



11

Table 42 Eu3+

Am3+



Table 43 Eu3+

Am3+



pH 4

Table 44 Eu3+

Am3+



pH 4


with GSH at

pHD 4















in the




in the






γ-radiation

12








in the






and Tb3+

samples at pH 4




and Tb3+




HDEHP in dodecane












kGy γ-radiation



kGy γ-radiation

13


after Eu3+





phases after Eu3+





Co

irradiator at DCF



present ()


ions

14

LIST OF FIGURES


phosphorescence


Ln3+

complexes






U into 92

Kr and

141

Ba
























15













of MA3+

and Ln3+








pD = 36


a) pD 7 [DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]



in D2O

at pD 36


2- in 41 vv



and [Cm(DTPA)]2-

in




concentration






16



2- (10 mM) with L-



in D2O at pD 3 with



in





395 nm at 298 K



395 nm


in H2O with and


nm




and Am3+

in the presence of











system


Y3+


mM LnY3+





17






pH 2

Figure 37 Eu3+

Am3+



Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



Figure 310 Eu3+

Am3+




-Ho3+

and Am3+

with 05 M L-



acid (bottom)




Figure 44 Eu3+

Am3+




Figure 45 Eu3+

Am3+




Figure 46 Eu3+

Am3+



tests




18




Figure 410 Eu3+

and Am3+




and Eu3+


repeat tests

Figure 411 Eu3+

and Am3+



for Eu3+


Am3+


Figure 412 Eu3+

and Am3+




and Eu3+


from 3 repeat tests






at 397 nm



at 397 nm


Eu3+











19






extraction




extraction










Eu3+



nm


extraction





extraction







397 nm


Eu3+



of 01-06 M

20












10

mM Dy3+


for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

21




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)









Figure 442 1H


Cys (bottom)









extraction






nm




nm

22




nm





Eu3+





Am3+




Am3+




Am3+






kerosene







kerosene






Figure 75 13


Figure 76 13


23

Figure 77 13


Figure 78 13


Figure 79 60



24

ABSTRACT



PhD


Separations

2015









) components




allowing Ln3+





















Eu3+

Am3+










Eu3+

Am3+




Am3+



processes

25

DECLARATION




26

COPYRIGHT STATEMENT
























27

ACKNOWLEDGEMENTS





new experience





Adam Swinburne



all of your help





















28




work














29


gt greater than

˂ less than


percent


α alpha

β beta

γ gamma

δ chemical shift

Δ change in


λ wavelength

microL microlitres

micros microseconds

ρ density

τ lifetime

ν frequency

ν= energy level

wavenumber

Aring angstroms





au arbitrary units


hydration sphere

Bq Becquerel

cm centimetres



E energy

F Faradays constant

30

g grams


Gy Gray

h Plancks constant

Hz Hertz

J Joules


K Kelvin

kBq kiloBecquerel

kg kilograms

kGy kiloGray

kJ kiloJoules

L litres


M molar (moldm-3

)

mg milligrams

MHz megaHertz

min minute(s)

mL millilitres

mm millimetres

mM millimolar

mol moles

mmol millimoles

ms milliseconds

ng nanograms

nm nanometres

ns nanoseconds




s seconds

t time


31


An actinides

aq aqueous





Alternatives


mass spectrometry




















EC electron capture




32





FP fission products


GSH glutathione






I ionic strength





IR infra-red





Lac lactate



Ln lanthanides



M metal

MA minor actinides


spectrometry

MOX mixed oxide



33

nIR near-infra-red




org organic













TEA triethylamine













UV ultra-violet




34



Alanine Ala

Arginine Arg

Asparagine Asn

Aspartic acid Asp

Cysteine Cys

Glutamic Acid Glu

Glutamine Gln

Glycine Gly

Histidine His

Isoleucine Ile

Leucine Leu

Lysine Lys

Methionine Met

Phenylalanine Phe

Proline Pro

Serine Ser

Threonine Thr

Tryptophan Trp

Tyrosine Tyr

Valine Val

35

1 INTRODUCTION


111 Background










the early 20th

















commercially5




36












238U (n γ)

239U rarr

239Np rarr

239Pu (n γ)

240Pu (n γ)

241Pu rarr

241Am (n γ)

242mAm rarr

242Cm



processes6




ions can be














ions relatively

readily

β- β

- β

- β

-


37



Configuration

(Metal)

Electron

Configuration

(Ln3+

)

3rd

Ionisation

Energy

(kJmol-1

)

4th

Ionisation

Energy

(kJmol-1

)


2 [Xe] 1850 4819

Ce Cerium [Xe]4f15d

16s

2 [Xe]4f

1 1949 3547


2 [Xe]4f

2 2086 3761


2 [Xe]4f

3 2130 3899


2 [Xe]4f

4 2150 3970


2 [Xe]4f

5 2260 3990


2 [Xe]4f

6 2404 4110


16s

2 [Xe]4f

7 1990 4250


2 [Xe]4f

8 2114 3839


6s2 [Xe]4f

9 2200 4001

Ho Holmium [Xe]4f11

6s2 [Xe]4f

10 2204 4100

Er Erbium [Xe]4f12

6s2 [Xe]4f

11 2194 4115

Tm Thulium [Xe]4f13

6s2 [Xe]4f

12 2285 4119


6s2 [Xe]4f

13 2415 4220


5d16s

2 [Xe]4f

14 2022 4360












to

An3+

and An3+

to An2+


38


An4+





subshell of Cm3+





Config

(Metal)

Electron

Config

(An2+

)

Electron

Config

(An3+

)

Electron

Config

(An4+

)


2 NA [Rn]6d

1 [Rn]


17s

2 NA [Rn]5f

2 [Rn]5f

1

U Uranium [Rn]5f36d

17s

2 NA [Rn]5f

3 [Rn]5f

2


17s

2 NA

[Rn]5f

4 [Rn]5f

3


2 NA [Rn]5f

5 [Rn]5f

4


2 [Rn]5f

7 [Rn]5f

6 [Rn]5f

5

Cm Curium [Rn]5f76d

17s

2 NA [Rn]5f

7 [Rn]5f

6


2 NA [Rn]5f

8 [Rn]5f

7


7s2 [Rn]5f

10 [Rn]5f

9 [Rn]5f

8


7s2 [Rn]5f

11 [Rn]5f

10 [Rn]5f

9

Fm Fermium [Rn]5f12

7s2 [Rn]5f

12 [Rn]5f

11 [Rn]5f

10


7s2 [Rn]5f

13 [Rn]5f

12 [Rn]5f

11


7s2 [Rn]5f

14 [Rn]5f

13 NA


6d17s

2 NA [Rn]5f

14 NA

39



unknown8







Equation 11





Equation 12






Equation 13

7 NpO23+

PuO23+

AmO65-

6 UO22+

NpO22+

PuO22+

AmO22

+5 PaO2

+UO2

+NpO2

+PuO2

+AmO2

+

4 Th4+

Pa4+

U4+

Np4+

Pu4+

Am4+

Cm4+

Bk4+

Cf4+

3 Ac3+

Th3+

Pa3+

U3+

Np3+

Pu3+

Am3+

Cm3+

Bk3+

Cf3+

Es3+

Fm3+

Md3+

No3+

Lr3+

2 Am2+

Cf2+

Es2+

Fm2+

Md2+

No2+



40

































ions allows them

41


solution






the lanthanides












and the An3+




ion The Am7+


conditions



lanthanides

1171 Hydrolysis



and An3+






+ H3O+




AnO2+ lt An

3+ lt AnO2

2+ lt An

4+

42


position of AnO22+









ions having a






aqueous solution12









+ EDTA4-









43








The



Equation 16






Equation 17

Equation 18













44














does not



luminescent

45




spectrum




Pr3+

Sm3+

Nd3+

Eu3+

Ho3+

Tb3+

Er3+

Dy3+

Yb3+

Tm3+

Gd3+

(UV)

Ce3+

(UV)










and Th4+


has a full 4f


performed on Fm3+

Md3+

or No2+



Am3+

and Cm3+




46




spectrum



of the spectrum

NpO22+

Pa4+

(UV) Pa4+

Pa4+

Pa4+

Pa4+

Am3+

U4+

(UV) U4+

Es3+

UO2+

UO22+

UO22+

UO22+

UO22+

Am3+

Am3+

Am3+

Am3+

Cm3+

Bk3+

Cf3+
























47





complexes 1S



ion 19







(2S+1)LJ










48

1226 Quenching












) thermal




Tb3+



is very high

(20500 cm-1


Eu3+





Ho3+

Er3+

Tm3+

Yb3+

Dy3+

and Sm3+

with


has the









chromophores

49


3H4

4I132

4I112

3H4

3H5

3H6

3H6

3H5

3H4

0

20000

4I92

4I112

4I132

4I152

4F32

2H92

4S32

4F92

2H112

4G52

4G72

4G92

(2D2P)32

4G1125D4

7F07F17F27F37F4

7F5

7F67F0

7F1

7F2

7F3

7F4

7F5

7F6

5D0

5D1

5D2

2F52

2F72

10000

6H52

6H72

6H92

6H112

6H132

4F32

4G52

4F32

4F12

4F52

4F72

4G72

4F92

4F112

3F2

3F4

3P0

3P1

3F3

1I6

1G4

4I92

4F92

4S32

4F72

3F4

3F3

3F2

1G4

E

cm

-1

=0

=1

=2

=3

=4

=5

=0

=1

=2

=3

=4

=5

=6

=7

2H112

1D2







Figure 14

50













Equation 19

Equation 110





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+


51


and A = 42 for Tb3+




for Eu3+


for Tb3+

242526

13 Nuclear Theory

131 Nuclear Power








15


U into 92

Kr and 141

Ba27






52







(~2 kJ mol-1


C or 2H)










of 235

U238























53







produced




The amount of waste







54











Constituent of SNF

U 956


Pu 09

Cs amp Sr (FP) 03

I amp Tc (FP) 01


MA 01










However the




ions with ligands35


and

Cm3+

from Ln3+

55











the species36




Equation 111

Equation 112



1341 PUREX







Equation 113 UO22+


Equation 114 PuO22+


56


corresponding Pu4+


(Equation 115)





and 117)









4+ to Pu

3+ with



-


The Pu3+







The process






57


treatment40



1342 TRUEX




58
















59


1343 DIAMEX









The nitric



Oxalic acid is











60




1344 SANEX











61









bipyridine)




62


1345 i-SANEX





and Cm3+


and Ln3+

ions are









process50









been proposed51

63

1346 GANEX









over Eu3+

gt 1000







For the











bipyridine)

64




phenanthroline)

65


1347 TRPO

















66










67


1348 LUCA





from Cm3+

Cf3+

and Ln3+

after co-extraction






concentrations55




68


1349 EXAm





from Cm3+






and Ln3+

in




Cm3+

and TEDGA is





69

137 TALSPEAK






(Am3+

and Cm3+

) from

Ln3+

and yttrium (Y3+












problem

1371 The Process






for Nd3+







Without DTPA Eu3+

Am3+





70



TALSPEAK Process







separation




and

Ln3+



DTPA5-





phosphate)


HEH[ϕP] ((2-(2-


71




The Ln3+


of the DTPA5-



MA[DTPA]2-


is bound




4 After the Ln3+





rate as the DTPA5-


allowing them to be


dissociates The





separation If Ln3+

and Y3+




the raffinate



and Es3+

but it



72


DTPA to M3+


extraction of Ln3+
















1 2

73


and Ln3+


60



An3+






chemistry62

74



















75






in storage









practicality




Initial research in
















have been explored

76


















77











1966 1 6-10














2188







Chem Rev 2014 266-267 171-193




78











Great Britain 1999









2012



Compounds 2000 303-304 137-141



Cambridge UK 2011



130-134


3373-3376




79


Extr Ion Exch 1985 31 75-109





1997 47 57-67














29 190








7 349-357




377


2010 28 3 287-312

80








2892-2893





282 523-526


50 7937-7939

81






























radiotherapy7

82







of LnDTPA2-


to take place For

LnDTPA2-




complexes






- 2348 for CmDTPA2-






2219 - 2085 for CmDTPA2-






Cm3+




83

strength to DTPA5-

than Eu3+


CmDTPA2-

than EuDTPA2-

(-407 kJ mol-1

vs -336 kJ mol-1

) determined by


to DTPA5-

than Eu3+


CmDTPA2-



in D2O for Cm3+




was







to the ligand









extraction as the

MDTPA2-











LnHDTPA- species


84


to MA3+


octadentate





and EuDTPA2-




than Eu3+


Cm3+






to MHDTPA-


than Eu3+

so



3+ This data is








H2O)










85

EUDTPAESP

15 10 5 0 -5 -10 -15 -20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

152

8

99

196

6

88

4

53

7

42

536

033

528

7

15

8

-01

1

-16

1

-40

6

-57

3-6

33

-105

3

-126

8

-148

3

-170

2

-184

7


2- in D2O at 278 K at pD = 36

DTPA pH71resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

199100215418

DEUTERIUM OXIDE

Water

38

1

34

033

833

632

8

30

630

530

3

a

86

DTPA pH361resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

204206100421

Water

47

647

5

38

5

35

634

634

434

3

31

531

431

2

DTPA pH21resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

202199100406

Water

47

5 46

9

39

0

35

4

34

033

933

7

31

130

930

8


[DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]




5- (005






Eu3+




ligand to Eu3+

ion at pH 361617



to DTPA5-


b

c

87


solvent molecules



in D2O at pD 36


(aq) and the

[Eu(DTPA)]2-







Equation 21

Equation 22





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+



and A = 42 for Tb3+


0

2

4

6

8

10

12

14

16

18

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

[Eu(DTPA)]2-

Eu3+

5D0 rarr 7F0

5D0 rarr 7F1

5D0 rarr 7F2

5D0 rarr 7F3

5D0 rarr 7F4

88

0075x) ms-1


and A =

5 ms and B = 006 ms-1

for Tb3+



ion is










ions

than Ln3+



and Cm3+

complexation



and Cm3+








the 241







The Am3+



89


but in this ion




the second J




Indeed


[Am(DTPA)xH2O]2-


7F1 excited







243Cm

3+ (015 microM Cm

3+ in 32



Cm3+




8S72


3+(aq)


in Cm3+


due to more

210 K

265 K

300 K

365 K

90





and [Cm(DTPA)]2-



Similarly to Eu3+


ion is known to





Equation 23













ions27

to form

40

45

50

55

60

65

70

75

80

570 590 610 630

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

Cm3+(aq)

[Cm(DTPA)]2-

91

M3+


3+-lactate

complexes

Equation 24a-c

(a)

(b)

(c)









5D0 rarr



ion changes as a









92

mode to Ln3+





28



ion and the








over Am3+

DTPA is required to


from Ln3+


holdback reagent



and M(Lac)n3-n

Studies carried






ternary M3+








93







ions32





668


and [M(DTPA)]2-






(bottom right)



1H




94

New Eu Ala0011resp

55 50 45 40 35 30 25 20 15 10 05 0


0

005

010

015

Norm

alized Inte

nsity

310100

CH3

CH

Water

47

147

1

35

5

12

712

6


278 K

Ala1resp

55 50 45 40 35 30 25 20 15 10 05 0


0

01

02

03

04

05

06

07

08

09

10

Norm

alized Inte

nsity

336100

CH3

CH

Water

36

536

336

2

13

3


95







EuDTPA Ala1esp

15 10 5 0 -5 -10 -15 -20


0005

0010

0015

0020

0025

0030

0035

Norm

alized Inte

nsity

150

5 96

892

185

2

75

4

50

4

39

533

231

625

8

14

6

05

0

-13

1

-44

2

-63

3-6

86

-108

2

-127

6

-143

1

-169

0

-183

9



at 278 K
















96


region (Figure 214)













0

100

200

300

400

500

600

700

0

5

10

15

20

25

30

220 320 420 520 620

Ab

sorp

tio

n In

ten

sity

(au

) Th

ou

san

ds

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

TbDTPA exc 379 nm




97

















seen in Table 21

0

2

4

6

8

10

12

14

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+

Eu-Lactate

Eu-Gly

Eu-Ala

Eu-Ser

98








metal







0

5

10

15

20

25

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser


Eu3+

011 165 89


Eu Gly 016 183 60

Eu Ala 016 187 60

Eu Ser 019 147 48

99


to [Eu(DTPA)]2-








seen in Table 22


with amino



upon


the Eu3+












Eu DTPA 063 230 23





100







Cm3+

to DTPA5-


[Cm(DTPA)]2-









processes33









40

45

50

55

60

65

70

75

80

570 580 590 600 610 620 630 640

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

[Cm(DTPA)]2-

[Cm(DTPA)]2- + Ala

101











from Am3+









32 33 34 3517

18

19

20

21

Alanine (pH 30)

Lactate ion (pH 60)

Lactic acid (pH 10)

ToC k M

-1 s

-1Error

1046 59E7 49E6

306 849E7 421E6

305 832E7 419E6

402 102E8 816E6




R2 = 0990

ln (

kM

-1 s

-1)

103Temp (K)

102


and Am3+




Am3+



not defined



pH 2 5620 5519 5132 5103

pH 3 1595 1653 1589 1252


The [Eu(DTPA)]2-




103










0

50

100

150

200

250

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

0

20

40

60

80

100

120

140

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

104








[Eu(DTPA)]2-




systems before and


τ of aqueous

phase

before

irradiation

(ms)

τ of aqueous

phase

after

irradiation

(ms)

τ of

organic

phase

before

irradiation

(ms)

τ of

organic

phase

after

irradiation

(ms)

Eu DTPA 063 066 222 262


Eu DTPA Gly 065 064 247 249

Eu DTPA Ala 065 065 211 238

Eu DTPA Ser 065 062 260 251

τ of

aqueous

phase

before

irr [H2O]

(ms)

τ of

aqueous

phase

after

irr[H2O]

(ms)

τ of

aqueous

phase

before irr

[D2O] (ms)

τ of

aqueous

phase

after irr

[D2O] (ms)

q

before

irr

q after

irr

Eu DTPA 063 066 230 227 11 10

Eu DTPA

Lactate

063 063 216 210 10 10

Eu DTPA

Gly

065 064 203 208 10 10

Eu DTPA

Ala

065 065 209 211 10 10

Eu DTPA

Ser

065 062 208 206 10 10

105











and [Eu(DTPA)]2-






ion when



and Cm3+



amino acidslactate


was





or Cm3+


[Eu(DTPA)]2-





106



2788


6445





107 758-769


1999 42 15 2988ndash2992





1968 10 94

11 I Bayat KFK



2013 101 221









89





107










271273 719





14547-14556


313-334




97 9 497-502







108


ACID BUFFERS












MA3+
























3 A pH 1 system

109



comparison

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring



Y3+


1 M


110












086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring


system

111










Lactic

Acid

10 3 0009 380 140 mdash 91







ions including Ln3+

and An3+

Aziz et al67


and Am3+

at pH 36












ion with



112


















113








H7DTPA2+


3+ and Ln






Ln3+

ions is H3DTPA2-

At pH 3 a much







INL

114







115





over Am3+













phase

y = -09383x - 15277 Rsup2 = 09854

y = -11258x + 01381 Rsup2 = 09289

-10

-05

00

05

10

15

20

-125 -12 -115 -11 -105 -1 -095

log

DEu

Am

log [Na5DTPA]

Am Extraction

Eu Extraction

116

Figure 37 Eu3+

Am3+


M) at pH 2










less Am3+







y = -08451x - 14757 Rsup2 = 09936

y = -07958x + 03998 Rsup2 = 0998

-15

-10

-05

00

05

10

15

-11 -1 -09 -08 -07 -06 -05 -04 -03

log

DEu

Am

log [Na5DTPA]


117

Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



y = 13522x + 02972 Rsup2 = 09283

y = 09682x + 19794 Rsup2 = 09561

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

y = 14702x + 00193 Rsup2 = 09981

y = 11892x + 17129 Rsup2 = 09713

-10

-05

00

05

10

15

20

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

118

Figure 310 Eu3+

Am3+













[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10




y = 11522x - 00047 Rsup2 = 09867

y = 12575x + 18424 Rsup2 = 09976

-10

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

119


[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 012 053 121 126 203

03 010 027 050 077 102

04 008 036 051 077 102



















in Table 35

120













Buffer pH DAm

DEu

SF

Lactic Acid 3 0009 0819 91


2 018 1016 57


2 053 4463 84

3 007 660 99

121


-Ho3+

and Am3+


pH 2 and pH 3






higher pH




Ln3+

Am3+











001

01

1

10

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

His pH 2

His pH 3

Am pH 2

Am pH 3

122












other amino acids

123


2014 32 378-390















2010 28 3 287-312

124


SYSTEM






in an aqueous

phase allowing Ln3+







industrial process









42)

125


(bottom)


vitamin B9 (bottom)






126














Ln3+

separation












to 751

for Ho3+









127



and Eu3+



















and Am3+

Over a



temperature







128

Figure 44 Eu3+

Am3+



tests

Figure 45 Eu3+

Am3+



tests




over Am3+


-02

0

02

04

06

08

1

12

14

16

18

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

-1

-08

-06

-04

-02

0

02

04

06

08

1

12

14

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

129










Figure 46 Eu3+

Am3+









-15

-10

-05

00

05

10

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

130

Table 41 Eu3+

Am3+


Na5DTPA at pH 4













131














4 (right)10

132











Figure 410 Eu3+

and Am3+



and Eu3+

Results


y = 19018x2 - 23123x + 72258 Rsup2 = 09937

y = 0442x2 - 03543x + 00659 Rsup2 = 0781

00

00

01

01

02

-20

-10

00

10

20

30

40

50

60

70

-01 26E-15 01 02 03 04 05 06 D

Am

DEu

[Na5DTPA] (M)

Eu extraction

Am extraction

133

Table 42 Eu3+

Am3+































134

Figure 411 Eu3+

and Am3+






Table 43 Eu3+

Am3+















y = -30649x2 + 3243x + 15029 Rsup2 = 09467

y = 00013x + 00015 Rsup2 = 08028

0000

0002

0004

0006

0008

0010

0012

0014

00

05

10

15

20

25

30

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

135

Figure 412 Eu3+

and Am3+



and Eu3+


Table 44 Eu3+

Am3+

















these conditions

y = -01882x + 08847 Rsup2 = 08326

y = 17968x - 04007 Rsup2 = 09946

-0500

0000

0500

1000

1500

2000

00

01

02

03

04

05

06

07

08

09

10

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

136



















0

1

2

3

4

5

6

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+ in H2O

Eu with GSH

Eu with DTPA

137

























in each case (q)

00

01

02

03

04

05

06

07

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

138


















00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

139


with GSH at pHD 4


[GSH]

(M)


01 1487 428 17

02 785 353 16

03 829 440 11

04 1545 161 58

05 1016 168 52







extraction at



Eu3+






00

01

01

02

02

03

03

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


140


ion is extracted as


spectrum11












00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

141










00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

142



J=1J=2

[GSH] (M)

01 02 03 04 05 st dev t-test

pD 2 0335 0399 0379 0375 0361 0024 No sig diff

pD 3 0440 0433 0451 0439 0419 0012 No sig diff

pD 4 0438 0467 0413 0469 0454 0023 No sig diff

st dev 0060 0034 0036 0048 0047

















143




pH 2 01 1699 plusmn 7 607 plusmn 9 10

pH 2 02 1692 plusmn 10 619 plusmn 10 09

pH 2 03 1686 plusmn 9 629 plusmn 9 09

pH 2 04 1636 plusmn 12 607 plusmn 13 09

pH 2 05 1596 plusmn 11 629 plusmn 13 09

pH 3 01 1755 plusmn 14 626 plusmn 7 09

pH 3 02 1737 plusmn 13 626 plusmn 15 09

pH 3 03 1723 plusmn 5 626 plusmn 13 09

pH 3 04 1720 plusmn 14 635 plusmn 17 09

pH 3 05 1677 plusmn 9 641 plusmn 14 09

pH 4 01 1778 plusmn 14 593 plusmn 16 10

pH 4 02 1747 plusmn 13 640 plusmn 15 09

pH 4 03 1679 plusmn 15 669 plusmn 18 08

pH 4 04 1689 plusmn 14 623 plusmn 15 09

pH 4 05 1679 plusmn 13 652 plusmn 19 08



complex The




GSH with the Eu3+







144















00

05

10

15

20

25

30

35

40

45

50

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Aq

03 M GSH pH 4 Aq

05 M GSH pH 4 Aq

05 M GSH pH 3 Aq

05 M GSH pH 2 Aq

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Org

03 M GSH pH 4 Org

05 M GSH pH 4 Org

05 M GSH pH 3 Org

05 M GSH pH 2 Org

145





as the HDEHPDEHP



ions GSH is




varied

J=1J=2

[GSH] (M)


pD 4 0202 0276 0247 0037 No sig diff

pD 3 - - 0100 - -

pD 2 - - 0500 - -

st dev - - 0202

t-test - - Sig diff







146










0

5

10

15

20

25

30

35

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

0

2

4

6

8

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

147



J=1J=2

[Na5DTPA] (M)

005 01 02 03 04 05 06 stdev t-test

D2O 0437 0441 0431 0437 0428 0425 0403 0013

No sig

diff

H2O 0450 0440 0437 0449 0422 0424 0428 0011

No sig

diff


















with GSH

148



[Na5DTPA]

(M)


005 1679 plusmn 3 652 plusmn 2 08

01 1549 plusmn 4 659 plusmn 2 10

02 1348 plusmn 4 666 plusmn 3 09

03 1179 plusmn 4 665 plusmn 3 08

04 1076 plusmn 4 674 plusmn 4 07

05 978 plusmn 4 698 plusmn 4 05

06 916 plusmn 5 714 plusmn 5 03






extraction with



0

1

2

3

4

5

6

7

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

149








phase





J=1J=2 0552 0578 0502 0039 No sig

diff






and 426

150














J=1J=2 0472 0499 0455 0510 0025 No sig

diff

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Aq

06 M HDEHP Aq

08 M HDEHP Aq

10 M HDEHP Aq

151





The lowest Eu3+



concentrations Am3+








Facility using a 60



seen in Figure 427

00

00

00

01

01

01

01

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Org

06 M HDEHP Org

08 M HDEHP Org

10 M HDEHP Org

152











00

01

01

02

02

03

03

04

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

153




[Na5DTPA] (M)

01 02 03 04 05 06 st

dev

t-test

J=1J=2 0477 0481 0452 0401 0407 0411 0036

No sig

diff



kGy γ-radiation


01 648 plusmn 4 1895 plusmn 12 10

02 661 plusmn 6 1678 plusmn 10 09

03 670 plusmn 6 1536 plusmn 11 08

04 679 plusmn 5 1462 plusmn 9 07

05 701 plusmn 7 1328 plusmn 10 05

06 696 plusmn 6 1211 plusmn 8 03






154


extraction from


range of 01-06 M















J=1J=2 0505 0563 0551 0031 No sig diff



under a variety



0

1

2

3

4

5

6

7

8

9

10

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Hu

nd

red

s

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

155



Also like Eu3+



441 Dy3+







is relatively








6H152 and

7F92 rarr







00

02

04

06

08

10

12

14

16

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O

Dy DTPA

Dy GSH

7F92 rarr

6H152

7F92 rarr

6H132

156







352 nm









lanthanides







00

02

04

06

08

10

12

14

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O Aq

Dy DTPA Aq

Dy GSH Aq

Dy H2O Org

Dy DTPA Org

Dy GSH Org

157



excitation







Systems at pH 4

The Dy3+



Eu3+

Tb3+

and Dy3+




irradiation





data

00

01

02

03

04

05

06

07

08

09

10

550 560 570 580 590

Emis

sio

n In

ten

sity

(au

) x 1

00

00

Wavelength (nm)

pH 2 Aq

pH 3 Aq

pH 4 Aq

pH 4 (03 M DTPA) Aq

pH 2 Org

pH 3 Org

pH 4 Org


158


10 mM Dy3+

) in H2O


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10 mM Dy3+

) with


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

0

5

10

15

20

25

30

35

40

45

50

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

0

2

4

6

8

10

12

14

16

18

20

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

159


10 mM Dy3+

005 M


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)








complex can also be

seen for the Tb3+



or Dy3+




Ln3+


Ln3+

with

GSH



0

1

2

3

4

5

6

7

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

160





and Tb3+

as calculations of

q for Sm3+

and Dy3+




ion with




and Tb3+

samples at pH 4


Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

Ln3+


Ln3+

with

GSH











and Tb3+

are as



161


10 mM Dy3+

) with


397

nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


pH range of 2-4







and Tb3+

samples before



Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)




00

10

20

30

40

50

60

70

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

162





with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

163


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)







and Dy3+



and Eu3+





the Ln3+



Ln3+


MS






00

05

10

15

20

25

30

35

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

164







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

0

5

10

15

20

25

30

35

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

165

















166



pH

[GSH]

(M)

SF


2 01 234 171 148 107 136 158 216 222 237 234

2 02 244 176 145 103 134 146 215 229 239 244

2 03 263 183 145 105 137 165 243 244 281 289

2 04 239 170 151 111 145 168 218 237 259 265

2 05 278 197 164 117 162 189 257 269 300 314

3 01 1735 972 477 276 163 104 112 53 41 38

3 02 1953 841 433 256 320 266 290 130 89 77

3 03 1898 785 388 220 152 90 95 39 28 24

3 04 2046 812 412 243 196 121 126 53 38 34

3 05 2145 705 312 139 36 16 20 04 02 00

4 01 3777 141 12 - - - - - - -

4 02 5548 231 36 06 - - - - - -

4 03 2768 239 27 - - - - - - -

4 04 1620 150 21 01 - - - - - -

4 05 1589 286 48 11 - - - - - -







167

GSH0011resp

45 40 35 30 25 20 15 10


0

005

010

Norm

alized Inte

nsity

197201200100200099

c

d

gb

i

f

44

944

844

6

38

9

37

637

437

2

28

628

628

528

4

24

924

824

724

624

524

4

21

120

920

720

5


45 40 35 30 25 20 15 10


0

005

010

015

020

025

Norm

alized Inte

nsity

133151244272014101206498131111059100

m

c

d

n

g

q

b

l

i

p

f

47

0

44

7 44

544

442

942

841

641

541

140

940

940

738

137

737

537

3

36

736

6

29

929

728

428

328

1

26

7

24

6

24

424

324

223

823

022

822

6

20

720

520

419

6

19

519

419

319

1

a

b

168

Eu GSH0011resp

45 40 35 30 25 20 15 10


005

010

015

Norm

alized Inte

nsity

035183050206177050088216024026100

d

g

b

i

f

c

45

044

844

7

42

0 41

841

741

341

241

138

0 37

837

737

136

9 30

230

1

28

928

728

628

428

328

1

25

124

924

724

624

424

2 23

3 23

122

921

020

820

720

519

919

819

719

6

GSH DTPA0011resp

45 40 35 30 25 20 15 10


0

005

010

015

Norm

alized Inte

nsity

032158045179156092075366021025099

c

d

g

DTPA

DTPA

DTPA

b

DTPA

i

f

45

044

9 44

744

6

41

941

841

741

241

141

0

37

937

737

537

036

8

34

133

633

5

30

730

530

1

28

928

628

528

428

228

0

25

024

824

624

524

324

1 23

223

022

821

020

820

620

419

719

5

c

d

169

EuDTPA GSH0011resp

45 40 35 30 25 20 15 10


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

180181200200212103673021100

47

0

44

244

1

38

4

36

836

3

32

832

0 30

230

129

9 28

628

528

328

1

24

724

624

524

424

3

20

820

720

520

3




Figure 442 1H





e

170













422)









and Am3+

when used without

Na5DTPA





Eu3+

and Am3+





experiments






171


extraction























with pH







conditions






172





irradiation











Dy3+




decreasing as


for Tb3+

and Dy3+


and Eu3+













173

















Chem B 2012 116 46 13722-13730


Chem 2010 8 4915-4920



174











) ions


by HDEHP (di-



considered






the MA3+



over Ln3+

This is













INE

175





















Protected

Protected Protected

176













0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

177






Eu3+




centre as expected


complexes at pD 2-4

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

0

5

10

15

20

25

30

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

178

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pD 2 0359 0381 0404 0353 0023

No sig

diff

pD 3 0394 0425 0417 0381 0020

No sig

diff

pD 4 0391 0427 0432 0423 0019

No sig

diff

st dev 0019 0026 0014 0035

t-test No sig

diff

No sig

diff

No sig

diff

No sig

diff












179



excitation

















itself








180




at 397 nm


extraction from



0

0

0

0

0

1

1

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

0

10

20

30

40

50

60

70

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


181


extraction from




extraction from



0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


0

1

2

3

4

5

6

7

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

Ala-DTPA Org

Arg-DTPA Org

His-DTPA Org

Ser-DTPA Org

182























Eu3+


pH 2-4

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pH 2 0208 0207 0198 0208 0005 No sig diff

pH 3 0210 0213 0311 0347 0069 Sig diff

pH 4 0182 0210 0206 0205 0013 No sig diff

st dev 0016 0003 0063 0081


183












397 nm





0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

184



DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-


J=1J=2 0357 0395 0412 0362 0026 No sig

diff













extraction from



0

1

2

3

4

5

6

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


185












DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

J=1J=2 0241 0233 0198 0231 0019

No sig

diff





without irradiation

(micros)


irradiation









186



Am + 152

Eu (1 kBq mL-1






and Eu3+








and Eu3+

for these











Am3+

using DTPA-


187


Am3+

using DTPA-



Am3+

using DTPA-




Am3+





and Am3+

can be seen in


Am3+

(as

188

Nd3+









189







190






complex to Eu3+





over Am3+





with the ligands








between Ln3+

Am3+






Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30








191






192





and MA3+




allowing Ln3+












from Ln3+

23









Ln3+




Am3+

is achieved








organic phase

193


keeping Am3+

















lanthanides



and [Eu(DTPA)]2-






Eu3+




ion when



and Cm3+





or Cm3+




194







and the



operation








and Am3+

when used without

Na5DTPA






Eu3+

and Am3+




the pH is increased







Am3+


TALSPEAK process



195

































can occur Further




Eu3+

Tb3+

and Dy3+






196




and Dy3+

which are


and Eu3+



-Ho3+






acid systems



Eu3+

Am3+









MA3+







at pH 2 3 and 4











irradiation



between Ln3+

Am3+


197





Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30



















the use of amino







with lactate15


Cm3+

with DTPA16


with





however there are



198

62 Future Work
















199




















and Cm3+














ratio of Am3+





200




10 245-279



523-526






2014 32 378-390





47 8856



2012 65 16 2862-2876











amino-acidshtm 2015




201
























were returned


amp An3+









202






Stock solutions




0625 M L-Phe in D2O







1 M amino








Equation 71









203







such as from a 60




H2O rarr H + OH

OH + Fe2+

rarr Fe3+

+ HO-

H + O2 rarr HO2

H+ + Fe

2+ + HO2 rarr Fe

3+ + H2O2

H2O2 + Fe2+

rarr Fe(OH)2+

+ OH

HO2 + Fe3+

rarr Fe2+

+ O2 + H+


ions to Fe3+

The amount

of Fe3+





out using the 60










72)2

204

Equation 72

Where


-1


cm-1









For γ-rays

εFe(III) = 2197 M-1

cm-1


Equation 73

Equation 74





205




min-1

)

1 1084678

2 1171864

3 1183066

4 1103841


INL









Stock solutions

1 M Na5DTPA in H2O

1 M L-Ala in H2O














206




















Stock solutions

1 M Na5DTPA in H2O











207






















732 Gamma counting










microL 241

Am or 154



208






Am or 154


) were also



733 ICP-MS




of each of La
























209

Stock solutions
























performed at INL







210


















(145 g 6 mmol)

Yields


)


)


)


)





[M+Na]+ and [M+K]






found in Appendix 6

211


+ 603 (39) [M+K]

+


+ 772 (9) [M+K]

+


+ 662 (15) [M+K]

+


+ 735 (10) [M+K]

+







spectra 13




1H









3JHH =100 Hz 4 H


4 H H2) 375 - 387 (m 4 H H3) 418 - 425 (m 2 H H1)


3JHH 730 Hz 4 H H9) 169 - 189


365 (s 6 H H7) 368 (s 2 H H6) 375 - 384 (m 4 H H3) 436 - 444 (m 2 H H1)



Hz 4 H H8) 452 (dd 3JHH =479 378 Hz 2 H H1)


(s 4 H H3) 358 (s 6 H H7) 362 (m 2 H H6) 370 - 375 (m 1 H H3) 464 - 466

(m 2 H H1) 714 (s 2 H H9) 843 (s 2 H H10)

212




213


7532 13

C NMR Spectroscopy




1718 (q-C C11) 1721 (q-C C10) 1746 (q-C C8)




C10) 1735 (q-C C8)



1693 (q-C C9) 1712 (q-C C10) 1717 (q-c C11) 1723 (CH3 C8)



1286 (q-C C13) 1333 (CH C15) 1711 (q-C C9) 1714 (q-C C11) 1716 (q-C

C10) 1746 (q-C C8)

214

Figure 75 13


Figure 76 13


Figure 77 13


215

Figure 78 13










C () H () N () Cl () Na ()


DTPA-(AlaOMe)2

4689 4224 662 685 1243 1146 0 475 0 0

DTPA-(ArgOMe)2

4583 3896 701 637 2100 1643 0 1427 0 0

DTPA-(SerOEt)2

4622 4300 663 755 1123 1041 0 240 0 0

DTPA-(HisOMe)2

4834 3985 594 668 1812 1458 0 595 0 0

216






Stock solutions



















using the 60






217

76 Instruments


Co Irradiator


Co



Co to 60







Figure 79 60













218


ions






20 minutes




400





Ln3+


Eu 617 395

Tb 545 379

Sm 600 403

Dy 575 352

219






220

APPENDICES








00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

221




00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

222







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

0

50

100

150

200

250

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

223


(1 mM)


mM)


DTPA-(AlaOMe)2 243

DTPA-(ArgOMe)2 238

DTPA-(SerOEt)2 240

DTPA-(HisOMe)2 286

224




0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

0

2

4

6

8

10

12

14

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

225


0

1

2

3

4

5

6

7

8

9

10

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

226







00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

tem

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

227



00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

228


[M+H]+

[M+Na]+ [M+K]

+

229

AP

PE

ND

IX 7

- 1H N

MR

spectru

m fo

r DT

PA

-(AlaO

Me)

2

230

GSH1ESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alize

d In

tensi

ty

Water

44

944

844

6

38

9

37

6 37

437

2 28

628

628

528

4

24

924

8 24

724

624

524

4

21

1 20

920

720

5

AP

PE

ND

IX 8

- 1H N

MR

spectru

m fo

r GS

H

231

EUGSHESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alized Inte

nsity

Water

45

044

844

7

41

8

38

037

837

7

37

136

9

30

230

1

28

7 28

628

4

24

9 24

724

624

423

323

1

21

020

820

720

5

AP

PE

ND

IX 8

a - 1H N

MR

spectru

m fo

r Eu(N

O3 )

3 + G

SH

232

4


and Ln-DTPA

Complexes


and Ln-DTPA

Complexes


and Ln-DTPA

Complexes


and [M(DTPA)]2-





Na5DTPA


Na5DTPA


Na5DTPA





References


Buffers












90

90

92

93

93

95

95

96

98

99

100

100

102

105

106

108

108

108

108

110

111

111

113

114

116

118

119

5




References


System





Na5DTPA


















441 Dy3+




Systems at pH 4



119

120

121

123

124

127

127

127

127

132

133

136

137

137

139

140

140

143

145

145

148

149

151

151

153

154

155

156

157

157

160

6




References



51 Ligand Synthesis











Work

References



62 Future Work

References





amp An3+

with amino acids in

TALSPEAK systems





163

166

170

173

174

175

176

176

179

183

183

184

185

186

187

190

191

192

192

198

200

201

201

201

201

201

201

202

202

7









amino acid studies


amino acid studies


acid studies



Na5DTPA


with Na5DTPA


GSH studies


amino acid studies

732 Gamma counting

733 ICP-MS


glutathione at UoM









MALDI-MS

203

203

203

205

205

205

205

205

206

206

206

206

207

207

207

208

208

208

208

209

209

210

210

210

210

8


NMR spectroscopy


7532 13

C NMR Spectroscopy


elemental analysis


ligands





76 Instruments


Co Irradiator






References

Appendices







(005 M) with Eu(NO3)3 (1 mM)





ligands


211

211

213

215

216

216

216

216

216

217

217

217

218

218

219

220

220

222

223

224

226

228

9





229

230

231

10

LIST OF TABLES








Reactors (LWR)


with amino

acidslactate




Am3+





[Eu(DTPA)]2-







system







values

Table 41 Eu3+

Am3+



11

Table 42 Eu3+

Am3+



Table 43 Eu3+

Am3+



pH 4

Table 44 Eu3+

Am3+



pH 4


with GSH at

pHD 4















in the




in the






γ-radiation

12








in the






and Tb3+

samples at pH 4




and Tb3+




HDEHP in dodecane












kGy γ-radiation



kGy γ-radiation

13


after Eu3+





phases after Eu3+





Co

irradiator at DCF



present ()


ions

14

LIST OF FIGURES


phosphorescence


Ln3+

complexes






U into 92

Kr and

141

Ba
























15













of MA3+

and Ln3+








pD = 36


a) pD 7 [DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]



in D2O

at pD 36


2- in 41 vv



and [Cm(DTPA)]2-

in




concentration






16



2- (10 mM) with L-



in D2O at pD 3 with



in





395 nm at 298 K



395 nm


in H2O with and


nm




and Am3+

in the presence of











system


Y3+


mM LnY3+





17






pH 2

Figure 37 Eu3+

Am3+



Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



Figure 310 Eu3+

Am3+




-Ho3+

and Am3+

with 05 M L-



acid (bottom)




Figure 44 Eu3+

Am3+




Figure 45 Eu3+

Am3+




Figure 46 Eu3+

Am3+



tests




18




Figure 410 Eu3+

and Am3+




and Eu3+


repeat tests

Figure 411 Eu3+

and Am3+



for Eu3+


Am3+


Figure 412 Eu3+

and Am3+




and Eu3+


from 3 repeat tests






at 397 nm



at 397 nm


Eu3+











19






extraction




extraction










Eu3+



nm


extraction





extraction







397 nm


Eu3+



of 01-06 M

20












10

mM Dy3+


for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

21




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)









Figure 442 1H


Cys (bottom)









extraction






nm




nm

22




nm





Eu3+





Am3+




Am3+




Am3+






kerosene







kerosene






Figure 75 13


Figure 76 13


23

Figure 77 13


Figure 78 13


Figure 79 60



24

ABSTRACT



PhD


Separations

2015









) components




allowing Ln3+





















Eu3+

Am3+










Eu3+

Am3+




Am3+



processes

25

DECLARATION




26

COPYRIGHT STATEMENT
























27

ACKNOWLEDGEMENTS





new experience





Adam Swinburne



all of your help





















28




work














29


gt greater than

˂ less than


percent


α alpha

β beta

γ gamma

δ chemical shift

Δ change in


λ wavelength

microL microlitres

micros microseconds

ρ density

τ lifetime

ν frequency

ν= energy level

wavenumber

Aring angstroms





au arbitrary units


hydration sphere

Bq Becquerel

cm centimetres



E energy

F Faradays constant

30

g grams


Gy Gray

h Plancks constant

Hz Hertz

J Joules


K Kelvin

kBq kiloBecquerel

kg kilograms

kGy kiloGray

kJ kiloJoules

L litres


M molar (moldm-3

)

mg milligrams

MHz megaHertz

min minute(s)

mL millilitres

mm millimetres

mM millimolar

mol moles

mmol millimoles

ms milliseconds

ng nanograms

nm nanometres

ns nanoseconds




s seconds

t time


31


An actinides

aq aqueous





Alternatives


mass spectrometry




















EC electron capture




32





FP fission products


GSH glutathione






I ionic strength





IR infra-red





Lac lactate



Ln lanthanides



M metal

MA minor actinides


spectrometry

MOX mixed oxide



33

nIR near-infra-red




org organic













TEA triethylamine













UV ultra-violet




34



Alanine Ala

Arginine Arg

Asparagine Asn

Aspartic acid Asp

Cysteine Cys

Glutamic Acid Glu

Glutamine Gln

Glycine Gly

Histidine His

Isoleucine Ile

Leucine Leu

Lysine Lys

Methionine Met

Phenylalanine Phe

Proline Pro

Serine Ser

Threonine Thr

Tryptophan Trp

Tyrosine Tyr

Valine Val

35

1 INTRODUCTION


111 Background










the early 20th

















commercially5




36












238U (n γ)

239U rarr

239Np rarr

239Pu (n γ)

240Pu (n γ)

241Pu rarr

241Am (n γ)

242mAm rarr

242Cm



processes6




ions can be














ions relatively

readily

β- β

- β

- β

-


37



Configuration

(Metal)

Electron

Configuration

(Ln3+

)

3rd

Ionisation

Energy

(kJmol-1

)

4th

Ionisation

Energy

(kJmol-1

)


2 [Xe] 1850 4819

Ce Cerium [Xe]4f15d

16s

2 [Xe]4f

1 1949 3547


2 [Xe]4f

2 2086 3761


2 [Xe]4f

3 2130 3899


2 [Xe]4f

4 2150 3970


2 [Xe]4f

5 2260 3990


2 [Xe]4f

6 2404 4110


16s

2 [Xe]4f

7 1990 4250


2 [Xe]4f

8 2114 3839


6s2 [Xe]4f

9 2200 4001

Ho Holmium [Xe]4f11

6s2 [Xe]4f

10 2204 4100

Er Erbium [Xe]4f12

6s2 [Xe]4f

11 2194 4115

Tm Thulium [Xe]4f13

6s2 [Xe]4f

12 2285 4119


6s2 [Xe]4f

13 2415 4220


5d16s

2 [Xe]4f

14 2022 4360












to

An3+

and An3+

to An2+


38


An4+





subshell of Cm3+





Config

(Metal)

Electron

Config

(An2+

)

Electron

Config

(An3+

)

Electron

Config

(An4+

)


2 NA [Rn]6d

1 [Rn]


17s

2 NA [Rn]5f

2 [Rn]5f

1

U Uranium [Rn]5f36d

17s

2 NA [Rn]5f

3 [Rn]5f

2


17s

2 NA

[Rn]5f

4 [Rn]5f

3


2 NA [Rn]5f

5 [Rn]5f

4


2 [Rn]5f

7 [Rn]5f

6 [Rn]5f

5

Cm Curium [Rn]5f76d

17s

2 NA [Rn]5f

7 [Rn]5f

6


2 NA [Rn]5f

8 [Rn]5f

7


7s2 [Rn]5f

10 [Rn]5f

9 [Rn]5f

8


7s2 [Rn]5f

11 [Rn]5f

10 [Rn]5f

9

Fm Fermium [Rn]5f12

7s2 [Rn]5f

12 [Rn]5f

11 [Rn]5f

10


7s2 [Rn]5f

13 [Rn]5f

12 [Rn]5f

11


7s2 [Rn]5f

14 [Rn]5f

13 NA


6d17s

2 NA [Rn]5f

14 NA

39



unknown8







Equation 11





Equation 12






Equation 13

7 NpO23+

PuO23+

AmO65-

6 UO22+

NpO22+

PuO22+

AmO22

+5 PaO2

+UO2

+NpO2

+PuO2

+AmO2

+

4 Th4+

Pa4+

U4+

Np4+

Pu4+

Am4+

Cm4+

Bk4+

Cf4+

3 Ac3+

Th3+

Pa3+

U3+

Np3+

Pu3+

Am3+

Cm3+

Bk3+

Cf3+

Es3+

Fm3+

Md3+

No3+

Lr3+

2 Am2+

Cf2+

Es2+

Fm2+

Md2+

No2+



40

































ions allows them

41


solution






the lanthanides












and the An3+




ion The Am7+


conditions



lanthanides

1171 Hydrolysis



and An3+






+ H3O+




AnO2+ lt An

3+ lt AnO2

2+ lt An

4+

42


position of AnO22+









ions having a






aqueous solution12









+ EDTA4-









43








The



Equation 16






Equation 17

Equation 18













44














does not



luminescent

45




spectrum




Pr3+

Sm3+

Nd3+

Eu3+

Ho3+

Tb3+

Er3+

Dy3+

Yb3+

Tm3+

Gd3+

(UV)

Ce3+

(UV)










and Th4+


has a full 4f


performed on Fm3+

Md3+

or No2+



Am3+

and Cm3+




46




spectrum



of the spectrum

NpO22+

Pa4+

(UV) Pa4+

Pa4+

Pa4+

Pa4+

Am3+

U4+

(UV) U4+

Es3+

UO2+

UO22+

UO22+

UO22+

UO22+

Am3+

Am3+

Am3+

Am3+

Cm3+

Bk3+

Cf3+
























47





complexes 1S



ion 19







(2S+1)LJ










48

1226 Quenching












) thermal




Tb3+



is very high

(20500 cm-1


Eu3+





Ho3+

Er3+

Tm3+

Yb3+

Dy3+

and Sm3+

with


has the









chromophores

49


3H4

4I132

4I112

3H4

3H5

3H6

3H6

3H5

3H4

0

20000

4I92

4I112

4I132

4I152

4F32

2H92

4S32

4F92

2H112

4G52

4G72

4G92

(2D2P)32

4G1125D4

7F07F17F27F37F4

7F5

7F67F0

7F1

7F2

7F3

7F4

7F5

7F6

5D0

5D1

5D2

2F52

2F72

10000

6H52

6H72

6H92

6H112

6H132

4F32

4G52

4F32

4F12

4F52

4F72

4G72

4F92

4F112

3F2

3F4

3P0

3P1

3F3

1I6

1G4

4I92

4F92

4S32

4F72

3F4

3F3

3F2

1G4

E

cm

-1

=0

=1

=2

=3

=4

=5

=0

=1

=2

=3

=4

=5

=6

=7

2H112

1D2







Figure 14

50













Equation 19

Equation 110





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+


51


and A = 42 for Tb3+




for Eu3+


for Tb3+

242526

13 Nuclear Theory

131 Nuclear Power








15


U into 92

Kr and 141

Ba27






52







(~2 kJ mol-1


C or 2H)










of 235

U238























53







produced




The amount of waste







54











Constituent of SNF

U 956


Pu 09

Cs amp Sr (FP) 03

I amp Tc (FP) 01


MA 01










However the




ions with ligands35


and

Cm3+

from Ln3+

55











the species36




Equation 111

Equation 112



1341 PUREX







Equation 113 UO22+


Equation 114 PuO22+


56


corresponding Pu4+


(Equation 115)





and 117)









4+ to Pu

3+ with



-


The Pu3+







The process






57


treatment40



1342 TRUEX




58
















59


1343 DIAMEX









The nitric



Oxalic acid is











60




1344 SANEX











61









bipyridine)




62


1345 i-SANEX





and Cm3+


and Ln3+

ions are









process50









been proposed51

63

1346 GANEX









over Eu3+

gt 1000







For the











bipyridine)

64




phenanthroline)

65


1347 TRPO

















66










67


1348 LUCA





from Cm3+

Cf3+

and Ln3+

after co-extraction






concentrations55




68


1349 EXAm





from Cm3+






and Ln3+

in




Cm3+

and TEDGA is





69

137 TALSPEAK






(Am3+

and Cm3+

) from

Ln3+

and yttrium (Y3+












problem

1371 The Process






for Nd3+







Without DTPA Eu3+

Am3+





70



TALSPEAK Process







separation




and

Ln3+



DTPA5-





phosphate)


HEH[ϕP] ((2-(2-


71




The Ln3+


of the DTPA5-



MA[DTPA]2-


is bound




4 After the Ln3+





rate as the DTPA5-


allowing them to be


dissociates The





separation If Ln3+

and Y3+




the raffinate



and Es3+

but it



72


DTPA to M3+


extraction of Ln3+
















1 2

73


and Ln3+


60



An3+






chemistry62

74



















75






in storage









practicality




Initial research in
















have been explored

76


















77











1966 1 6-10














2188







Chem Rev 2014 266-267 171-193




78











Great Britain 1999









2012



Compounds 2000 303-304 137-141



Cambridge UK 2011



130-134


3373-3376




79


Extr Ion Exch 1985 31 75-109





1997 47 57-67














29 190








7 349-357




377


2010 28 3 287-312

80








2892-2893





282 523-526


50 7937-7939

81






























radiotherapy7

82







of LnDTPA2-


to take place For

LnDTPA2-




complexes






- 2348 for CmDTPA2-






2219 - 2085 for CmDTPA2-






Cm3+




83

strength to DTPA5-

than Eu3+


CmDTPA2-

than EuDTPA2-

(-407 kJ mol-1

vs -336 kJ mol-1

) determined by


to DTPA5-

than Eu3+


CmDTPA2-



in D2O for Cm3+




was







to the ligand









extraction as the

MDTPA2-











LnHDTPA- species


84


to MA3+


octadentate





and EuDTPA2-




than Eu3+


Cm3+






to MHDTPA-


than Eu3+

so



3+ This data is








H2O)










85

EUDTPAESP

15 10 5 0 -5 -10 -15 -20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

152

8

99

196

6

88

4

53

7

42

536

033

528

7

15

8

-01

1

-16

1

-40

6

-57

3-6

33

-105

3

-126

8

-148

3

-170

2

-184

7


2- in D2O at 278 K at pD = 36

DTPA pH71resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

199100215418

DEUTERIUM OXIDE

Water

38

1

34

033

833

632

8

30

630

530

3

a

86

DTPA pH361resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

204206100421

Water

47

647

5

38

5

35

634

634

434

3

31

531

431

2

DTPA pH21resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

202199100406

Water

47

5 46

9

39

0

35

4

34

033

933

7

31

130

930

8


[DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]




5- (005






Eu3+




ligand to Eu3+

ion at pH 361617



to DTPA5-


b

c

87


solvent molecules



in D2O at pD 36


(aq) and the

[Eu(DTPA)]2-







Equation 21

Equation 22





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+



and A = 42 for Tb3+


0

2

4

6

8

10

12

14

16

18

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

[Eu(DTPA)]2-

Eu3+

5D0 rarr 7F0

5D0 rarr 7F1

5D0 rarr 7F2

5D0 rarr 7F3

5D0 rarr 7F4

88

0075x) ms-1


and A =

5 ms and B = 006 ms-1

for Tb3+



ion is










ions

than Ln3+



and Cm3+

complexation



and Cm3+








the 241







The Am3+



89


but in this ion




the second J




Indeed


[Am(DTPA)xH2O]2-


7F1 excited







243Cm

3+ (015 microM Cm

3+ in 32



Cm3+




8S72


3+(aq)


in Cm3+


due to more

210 K

265 K

300 K

365 K

90





and [Cm(DTPA)]2-



Similarly to Eu3+


ion is known to





Equation 23













ions27

to form

40

45

50

55

60

65

70

75

80

570 590 610 630

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

Cm3+(aq)

[Cm(DTPA)]2-

91

M3+


3+-lactate

complexes

Equation 24a-c

(a)

(b)

(c)









5D0 rarr



ion changes as a









92

mode to Ln3+





28



ion and the








over Am3+

DTPA is required to


from Ln3+


holdback reagent



and M(Lac)n3-n

Studies carried






ternary M3+








93







ions32





668


and [M(DTPA)]2-






(bottom right)



1H




94

New Eu Ala0011resp

55 50 45 40 35 30 25 20 15 10 05 0


0

005

010

015

Norm

alized Inte

nsity

310100

CH3

CH

Water

47

147

1

35

5

12

712

6


278 K

Ala1resp

55 50 45 40 35 30 25 20 15 10 05 0


0

01

02

03

04

05

06

07

08

09

10

Norm

alized Inte

nsity

336100

CH3

CH

Water

36

536

336

2

13

3


95







EuDTPA Ala1esp

15 10 5 0 -5 -10 -15 -20


0005

0010

0015

0020

0025

0030

0035

Norm

alized Inte

nsity

150

5 96

892

185

2

75

4

50

4

39

533

231

625

8

14

6

05

0

-13

1

-44

2

-63

3-6

86

-108

2

-127

6

-143

1

-169

0

-183

9



at 278 K
















96


region (Figure 214)













0

100

200

300

400

500

600

700

0

5

10

15

20

25

30

220 320 420 520 620

Ab

sorp

tio

n In

ten

sity

(au

) Th

ou

san

ds

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

TbDTPA exc 379 nm




97

















seen in Table 21

0

2

4

6

8

10

12

14

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+

Eu-Lactate

Eu-Gly

Eu-Ala

Eu-Ser

98








metal







0

5

10

15

20

25

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser


Eu3+

011 165 89


Eu Gly 016 183 60

Eu Ala 016 187 60

Eu Ser 019 147 48

99


to [Eu(DTPA)]2-








seen in Table 22


with amino



upon


the Eu3+












Eu DTPA 063 230 23





100







Cm3+

to DTPA5-


[Cm(DTPA)]2-









processes33









40

45

50

55

60

65

70

75

80

570 580 590 600 610 620 630 640

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

[Cm(DTPA)]2-

[Cm(DTPA)]2- + Ala

101











from Am3+









32 33 34 3517

18

19

20

21

Alanine (pH 30)

Lactate ion (pH 60)

Lactic acid (pH 10)

ToC k M

-1 s

-1Error

1046 59E7 49E6

306 849E7 421E6

305 832E7 419E6

402 102E8 816E6




R2 = 0990

ln (

kM

-1 s

-1)

103Temp (K)

102


and Am3+




Am3+



not defined



pH 2 5620 5519 5132 5103

pH 3 1595 1653 1589 1252


The [Eu(DTPA)]2-




103










0

50

100

150

200

250

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

0

20

40

60

80

100

120

140

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

104








[Eu(DTPA)]2-




systems before and


τ of aqueous

phase

before

irradiation

(ms)

τ of aqueous

phase

after

irradiation

(ms)

τ of

organic

phase

before

irradiation

(ms)

τ of

organic

phase

after

irradiation

(ms)

Eu DTPA 063 066 222 262


Eu DTPA Gly 065 064 247 249

Eu DTPA Ala 065 065 211 238

Eu DTPA Ser 065 062 260 251

τ of

aqueous

phase

before

irr [H2O]

(ms)

τ of

aqueous

phase

after

irr[H2O]

(ms)

τ of

aqueous

phase

before irr

[D2O] (ms)

τ of

aqueous

phase

after irr

[D2O] (ms)

q

before

irr

q after

irr

Eu DTPA 063 066 230 227 11 10

Eu DTPA

Lactate

063 063 216 210 10 10

Eu DTPA

Gly

065 064 203 208 10 10

Eu DTPA

Ala

065 065 209 211 10 10

Eu DTPA

Ser

065 062 208 206 10 10

105











and [Eu(DTPA)]2-






ion when



and Cm3+



amino acidslactate


was





or Cm3+


[Eu(DTPA)]2-





106



2788


6445





107 758-769


1999 42 15 2988ndash2992





1968 10 94

11 I Bayat KFK



2013 101 221









89





107










271273 719





14547-14556


313-334




97 9 497-502







108


ACID BUFFERS












MA3+
























3 A pH 1 system

109



comparison

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring



Y3+


1 M


110












086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring


system

111










Lactic

Acid

10 3 0009 380 140 mdash 91







ions including Ln3+

and An3+

Aziz et al67


and Am3+

at pH 36












ion with



112


















113








H7DTPA2+


3+ and Ln






Ln3+

ions is H3DTPA2-

At pH 3 a much







INL

114







115





over Am3+













phase

y = -09383x - 15277 Rsup2 = 09854

y = -11258x + 01381 Rsup2 = 09289

-10

-05

00

05

10

15

20

-125 -12 -115 -11 -105 -1 -095

log

DEu

Am

log [Na5DTPA]

Am Extraction

Eu Extraction

116

Figure 37 Eu3+

Am3+


M) at pH 2










less Am3+







y = -08451x - 14757 Rsup2 = 09936

y = -07958x + 03998 Rsup2 = 0998

-15

-10

-05

00

05

10

15

-11 -1 -09 -08 -07 -06 -05 -04 -03

log

DEu

Am

log [Na5DTPA]


117

Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



y = 13522x + 02972 Rsup2 = 09283

y = 09682x + 19794 Rsup2 = 09561

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

y = 14702x + 00193 Rsup2 = 09981

y = 11892x + 17129 Rsup2 = 09713

-10

-05

00

05

10

15

20

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

118

Figure 310 Eu3+

Am3+













[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10




y = 11522x - 00047 Rsup2 = 09867

y = 12575x + 18424 Rsup2 = 09976

-10

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

119


[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 012 053 121 126 203

03 010 027 050 077 102

04 008 036 051 077 102



















in Table 35

120













Buffer pH DAm

DEu

SF

Lactic Acid 3 0009 0819 91


2 018 1016 57


2 053 4463 84

3 007 660 99

121


-Ho3+

and Am3+


pH 2 and pH 3






higher pH




Ln3+

Am3+











001

01

1

10

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

His pH 2

His pH 3

Am pH 2

Am pH 3

122












other amino acids

123


2014 32 378-390















2010 28 3 287-312

124


SYSTEM






in an aqueous

phase allowing Ln3+







industrial process









42)

125


(bottom)


vitamin B9 (bottom)






126














Ln3+

separation












to 751

for Ho3+









127



and Eu3+



















and Am3+

Over a



temperature







128

Figure 44 Eu3+

Am3+



tests

Figure 45 Eu3+

Am3+



tests




over Am3+


-02

0

02

04

06

08

1

12

14

16

18

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

-1

-08

-06

-04

-02

0

02

04

06

08

1

12

14

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

129










Figure 46 Eu3+

Am3+









-15

-10

-05

00

05

10

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

130

Table 41 Eu3+

Am3+


Na5DTPA at pH 4













131














4 (right)10

132











Figure 410 Eu3+

and Am3+



and Eu3+

Results


y = 19018x2 - 23123x + 72258 Rsup2 = 09937

y = 0442x2 - 03543x + 00659 Rsup2 = 0781

00

00

01

01

02

-20

-10

00

10

20

30

40

50

60

70

-01 26E-15 01 02 03 04 05 06 D

Am

DEu

[Na5DTPA] (M)

Eu extraction

Am extraction

133

Table 42 Eu3+

Am3+































134

Figure 411 Eu3+

and Am3+






Table 43 Eu3+

Am3+















y = -30649x2 + 3243x + 15029 Rsup2 = 09467

y = 00013x + 00015 Rsup2 = 08028

0000

0002

0004

0006

0008

0010

0012

0014

00

05

10

15

20

25

30

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

135

Figure 412 Eu3+

and Am3+



and Eu3+


Table 44 Eu3+

Am3+

















these conditions

y = -01882x + 08847 Rsup2 = 08326

y = 17968x - 04007 Rsup2 = 09946

-0500

0000

0500

1000

1500

2000

00

01

02

03

04

05

06

07

08

09

10

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

136



















0

1

2

3

4

5

6

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+ in H2O

Eu with GSH

Eu with DTPA

137

























in each case (q)

00

01

02

03

04

05

06

07

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

138


















00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

139


with GSH at pHD 4


[GSH]

(M)


01 1487 428 17

02 785 353 16

03 829 440 11

04 1545 161 58

05 1016 168 52







extraction at



Eu3+






00

01

01

02

02

03

03

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


140


ion is extracted as


spectrum11












00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

141










00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

142



J=1J=2

[GSH] (M)

01 02 03 04 05 st dev t-test

pD 2 0335 0399 0379 0375 0361 0024 No sig diff

pD 3 0440 0433 0451 0439 0419 0012 No sig diff

pD 4 0438 0467 0413 0469 0454 0023 No sig diff

st dev 0060 0034 0036 0048 0047

















143




pH 2 01 1699 plusmn 7 607 plusmn 9 10

pH 2 02 1692 plusmn 10 619 plusmn 10 09

pH 2 03 1686 plusmn 9 629 plusmn 9 09

pH 2 04 1636 plusmn 12 607 plusmn 13 09

pH 2 05 1596 plusmn 11 629 plusmn 13 09

pH 3 01 1755 plusmn 14 626 plusmn 7 09

pH 3 02 1737 plusmn 13 626 plusmn 15 09

pH 3 03 1723 plusmn 5 626 plusmn 13 09

pH 3 04 1720 plusmn 14 635 plusmn 17 09

pH 3 05 1677 plusmn 9 641 plusmn 14 09

pH 4 01 1778 plusmn 14 593 plusmn 16 10

pH 4 02 1747 plusmn 13 640 plusmn 15 09

pH 4 03 1679 plusmn 15 669 plusmn 18 08

pH 4 04 1689 plusmn 14 623 plusmn 15 09

pH 4 05 1679 plusmn 13 652 plusmn 19 08



complex The




GSH with the Eu3+







144















00

05

10

15

20

25

30

35

40

45

50

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Aq

03 M GSH pH 4 Aq

05 M GSH pH 4 Aq

05 M GSH pH 3 Aq

05 M GSH pH 2 Aq

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Org

03 M GSH pH 4 Org

05 M GSH pH 4 Org

05 M GSH pH 3 Org

05 M GSH pH 2 Org

145





as the HDEHPDEHP



ions GSH is




varied

J=1J=2

[GSH] (M)


pD 4 0202 0276 0247 0037 No sig diff

pD 3 - - 0100 - -

pD 2 - - 0500 - -

st dev - - 0202

t-test - - Sig diff







146










0

5

10

15

20

25

30

35

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

0

2

4

6

8

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

147



J=1J=2

[Na5DTPA] (M)

005 01 02 03 04 05 06 stdev t-test

D2O 0437 0441 0431 0437 0428 0425 0403 0013

No sig

diff

H2O 0450 0440 0437 0449 0422 0424 0428 0011

No sig

diff


















with GSH

148



[Na5DTPA]

(M)


005 1679 plusmn 3 652 plusmn 2 08

01 1549 plusmn 4 659 plusmn 2 10

02 1348 plusmn 4 666 plusmn 3 09

03 1179 plusmn 4 665 plusmn 3 08

04 1076 plusmn 4 674 plusmn 4 07

05 978 plusmn 4 698 plusmn 4 05

06 916 plusmn 5 714 plusmn 5 03






extraction with



0

1

2

3

4

5

6

7

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

149








phase





J=1J=2 0552 0578 0502 0039 No sig

diff






and 426

150














J=1J=2 0472 0499 0455 0510 0025 No sig

diff

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Aq

06 M HDEHP Aq

08 M HDEHP Aq

10 M HDEHP Aq

151





The lowest Eu3+



concentrations Am3+








Facility using a 60



seen in Figure 427

00

00

00

01

01

01

01

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Org

06 M HDEHP Org

08 M HDEHP Org

10 M HDEHP Org

152











00

01

01

02

02

03

03

04

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

153




[Na5DTPA] (M)

01 02 03 04 05 06 st

dev

t-test

J=1J=2 0477 0481 0452 0401 0407 0411 0036

No sig

diff



kGy γ-radiation


01 648 plusmn 4 1895 plusmn 12 10

02 661 plusmn 6 1678 plusmn 10 09

03 670 plusmn 6 1536 plusmn 11 08

04 679 plusmn 5 1462 plusmn 9 07

05 701 plusmn 7 1328 plusmn 10 05

06 696 plusmn 6 1211 plusmn 8 03






154


extraction from


range of 01-06 M















J=1J=2 0505 0563 0551 0031 No sig diff



under a variety



0

1

2

3

4

5

6

7

8

9

10

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Hu

nd

red

s

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

155



Also like Eu3+



441 Dy3+







is relatively








6H152 and

7F92 rarr







00

02

04

06

08

10

12

14

16

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O

Dy DTPA

Dy GSH

7F92 rarr

6H152

7F92 rarr

6H132

156







352 nm









lanthanides







00

02

04

06

08

10

12

14

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O Aq

Dy DTPA Aq

Dy GSH Aq

Dy H2O Org

Dy DTPA Org

Dy GSH Org

157



excitation







Systems at pH 4

The Dy3+



Eu3+

Tb3+

and Dy3+




irradiation





data

00

01

02

03

04

05

06

07

08

09

10

550 560 570 580 590

Emis

sio

n In

ten

sity

(au

) x 1

00

00

Wavelength (nm)

pH 2 Aq

pH 3 Aq

pH 4 Aq

pH 4 (03 M DTPA) Aq

pH 2 Org

pH 3 Org

pH 4 Org


158


10 mM Dy3+

) in H2O


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10 mM Dy3+

) with


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

0

5

10

15

20

25

30

35

40

45

50

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

0

2

4

6

8

10

12

14

16

18

20

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

159


10 mM Dy3+

005 M


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)








complex can also be

seen for the Tb3+



or Dy3+




Ln3+


Ln3+

with

GSH



0

1

2

3

4

5

6

7

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

160





and Tb3+

as calculations of

q for Sm3+

and Dy3+




ion with




and Tb3+

samples at pH 4


Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

Ln3+


Ln3+

with

GSH











and Tb3+

are as



161


10 mM Dy3+

) with


397

nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


pH range of 2-4







and Tb3+

samples before



Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)




00

10

20

30

40

50

60

70

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

162





with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

163


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)







and Dy3+



and Eu3+





the Ln3+



Ln3+


MS






00

05

10

15

20

25

30

35

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

164







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

0

5

10

15

20

25

30

35

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

165

















166



pH

[GSH]

(M)

SF


2 01 234 171 148 107 136 158 216 222 237 234

2 02 244 176 145 103 134 146 215 229 239 244

2 03 263 183 145 105 137 165 243 244 281 289

2 04 239 170 151 111 145 168 218 237 259 265

2 05 278 197 164 117 162 189 257 269 300 314

3 01 1735 972 477 276 163 104 112 53 41 38

3 02 1953 841 433 256 320 266 290 130 89 77

3 03 1898 785 388 220 152 90 95 39 28 24

3 04 2046 812 412 243 196 121 126 53 38 34

3 05 2145 705 312 139 36 16 20 04 02 00

4 01 3777 141 12 - - - - - - -

4 02 5548 231 36 06 - - - - - -

4 03 2768 239 27 - - - - - - -

4 04 1620 150 21 01 - - - - - -

4 05 1589 286 48 11 - - - - - -







167

GSH0011resp

45 40 35 30 25 20 15 10


0

005

010

Norm

alized Inte

nsity

197201200100200099

c

d

gb

i

f

44

944

844

6

38

9

37

637

437

2

28

628

628

528

4

24

924

824

724

624

524

4

21

120

920

720

5


45 40 35 30 25 20 15 10


0

005

010

015

020

025

Norm

alized Inte

nsity

133151244272014101206498131111059100

m

c

d

n

g

q

b

l

i

p

f

47

0

44

7 44

544

442

942

841

641

541

140

940

940

738

137

737

537

3

36

736

6

29

929

728

428

328

1

26

7

24

6

24

424

324

223

823

022

822

6

20

720

520

419

6

19

519

419

319

1

a

b

168

Eu GSH0011resp

45 40 35 30 25 20 15 10


005

010

015

Norm

alized Inte

nsity

035183050206177050088216024026100

d

g

b

i

f

c

45

044

844

7

42

0 41

841

741

341

241

138

0 37

837

737

136

9 30

230

1

28

928

728

628

428

328

1

25

124

924

724

624

424

2 23

3 23

122

921

020

820

720

519

919

819

719

6

GSH DTPA0011resp

45 40 35 30 25 20 15 10


0

005

010

015

Norm

alized Inte

nsity

032158045179156092075366021025099

c

d

g

DTPA

DTPA

DTPA

b

DTPA

i

f

45

044

9 44

744

6

41

941

841

741

241

141

0

37

937

737

537

036

8

34

133

633

5

30

730

530

1

28

928

628

528

428

228

0

25

024

824

624

524

324

1 23

223

022

821

020

820

620

419

719

5

c

d

169

EuDTPA GSH0011resp

45 40 35 30 25 20 15 10


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

180181200200212103673021100

47

0

44

244

1

38

4

36

836

3

32

832

0 30

230

129

9 28

628

528

328

1

24

724

624

524

424

3

20

820

720

520

3




Figure 442 1H





e

170













422)









and Am3+

when used without

Na5DTPA





Eu3+

and Am3+





experiments






171


extraction























with pH







conditions






172





irradiation











Dy3+




decreasing as


for Tb3+

and Dy3+


and Eu3+













173

















Chem B 2012 116 46 13722-13730


Chem 2010 8 4915-4920



174











) ions


by HDEHP (di-



considered






the MA3+



over Ln3+

This is













INE

175





















Protected

Protected Protected

176













0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

177






Eu3+




centre as expected


complexes at pD 2-4

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

0

5

10

15

20

25

30

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

178

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pD 2 0359 0381 0404 0353 0023

No sig

diff

pD 3 0394 0425 0417 0381 0020

No sig

diff

pD 4 0391 0427 0432 0423 0019

No sig

diff

st dev 0019 0026 0014 0035

t-test No sig

diff

No sig

diff

No sig

diff

No sig

diff












179



excitation

















itself








180




at 397 nm


extraction from



0

0

0

0

0

1

1

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

0

10

20

30

40

50

60

70

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


181


extraction from




extraction from



0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


0

1

2

3

4

5

6

7

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

Ala-DTPA Org

Arg-DTPA Org

His-DTPA Org

Ser-DTPA Org

182























Eu3+


pH 2-4

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pH 2 0208 0207 0198 0208 0005 No sig diff

pH 3 0210 0213 0311 0347 0069 Sig diff

pH 4 0182 0210 0206 0205 0013 No sig diff

st dev 0016 0003 0063 0081


183












397 nm





0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

184



DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-


J=1J=2 0357 0395 0412 0362 0026 No sig

diff













extraction from



0

1

2

3

4

5

6

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


185












DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

J=1J=2 0241 0233 0198 0231 0019

No sig

diff





without irradiation

(micros)


irradiation









186



Am + 152

Eu (1 kBq mL-1






and Eu3+








and Eu3+

for these











Am3+

using DTPA-


187


Am3+

using DTPA-



Am3+

using DTPA-




Am3+





and Am3+

can be seen in


Am3+

(as

188

Nd3+









189







190






complex to Eu3+





over Am3+





with the ligands








between Ln3+

Am3+






Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30








191






192





and MA3+




allowing Ln3+












from Ln3+

23









Ln3+




Am3+

is achieved








organic phase

193


keeping Am3+

















lanthanides



and [Eu(DTPA)]2-






Eu3+




ion when



and Cm3+





or Cm3+




194







and the



operation








and Am3+

when used without

Na5DTPA






Eu3+

and Am3+




the pH is increased







Am3+


TALSPEAK process



195

































can occur Further




Eu3+

Tb3+

and Dy3+






196




and Dy3+

which are


and Eu3+



-Ho3+






acid systems



Eu3+

Am3+









MA3+







at pH 2 3 and 4











irradiation



between Ln3+

Am3+


197





Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30



















the use of amino







with lactate15


Cm3+

with DTPA16


with





however there are



198

62 Future Work
















199




















and Cm3+














ratio of Am3+





200




10 245-279



523-526






2014 32 378-390





47 8856



2012 65 16 2862-2876











amino-acidshtm 2015




201
























were returned


amp An3+









202






Stock solutions




0625 M L-Phe in D2O







1 M amino








Equation 71









203







such as from a 60




H2O rarr H + OH

OH + Fe2+

rarr Fe3+

+ HO-

H + O2 rarr HO2

H+ + Fe

2+ + HO2 rarr Fe

3+ + H2O2

H2O2 + Fe2+

rarr Fe(OH)2+

+ OH

HO2 + Fe3+

rarr Fe2+

+ O2 + H+


ions to Fe3+

The amount

of Fe3+





out using the 60










72)2

204

Equation 72

Where


-1


cm-1









For γ-rays

εFe(III) = 2197 M-1

cm-1


Equation 73

Equation 74





205




min-1

)

1 1084678

2 1171864

3 1183066

4 1103841


INL









Stock solutions

1 M Na5DTPA in H2O

1 M L-Ala in H2O














206




















Stock solutions

1 M Na5DTPA in H2O











207






















732 Gamma counting










microL 241

Am or 154



208






Am or 154


) were also



733 ICP-MS




of each of La
























209

Stock solutions
























performed at INL







210


















(145 g 6 mmol)

Yields


)


)


)


)





[M+Na]+ and [M+K]






found in Appendix 6

211


+ 603 (39) [M+K]

+


+ 772 (9) [M+K]

+


+ 662 (15) [M+K]

+


+ 735 (10) [M+K]

+







spectra 13




1H









3JHH =100 Hz 4 H


4 H H2) 375 - 387 (m 4 H H3) 418 - 425 (m 2 H H1)


3JHH 730 Hz 4 H H9) 169 - 189


365 (s 6 H H7) 368 (s 2 H H6) 375 - 384 (m 4 H H3) 436 - 444 (m 2 H H1)



Hz 4 H H8) 452 (dd 3JHH =479 378 Hz 2 H H1)


(s 4 H H3) 358 (s 6 H H7) 362 (m 2 H H6) 370 - 375 (m 1 H H3) 464 - 466

(m 2 H H1) 714 (s 2 H H9) 843 (s 2 H H10)

212




213


7532 13

C NMR Spectroscopy




1718 (q-C C11) 1721 (q-C C10) 1746 (q-C C8)




C10) 1735 (q-C C8)



1693 (q-C C9) 1712 (q-C C10) 1717 (q-c C11) 1723 (CH3 C8)



1286 (q-C C13) 1333 (CH C15) 1711 (q-C C9) 1714 (q-C C11) 1716 (q-C

C10) 1746 (q-C C8)

214

Figure 75 13


Figure 76 13


Figure 77 13


215

Figure 78 13










C () H () N () Cl () Na ()


DTPA-(AlaOMe)2

4689 4224 662 685 1243 1146 0 475 0 0

DTPA-(ArgOMe)2

4583 3896 701 637 2100 1643 0 1427 0 0

DTPA-(SerOEt)2

4622 4300 663 755 1123 1041 0 240 0 0

DTPA-(HisOMe)2

4834 3985 594 668 1812 1458 0 595 0 0

216






Stock solutions



















using the 60






217

76 Instruments


Co Irradiator


Co



Co to 60







Figure 79 60













218


ions






20 minutes




400





Ln3+


Eu 617 395

Tb 545 379

Sm 600 403

Dy 575 352

219






220

APPENDICES








00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

221




00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

222







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

0

50

100

150

200

250

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

223


(1 mM)


mM)


DTPA-(AlaOMe)2 243

DTPA-(ArgOMe)2 238

DTPA-(SerOEt)2 240

DTPA-(HisOMe)2 286

224




0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

0

2

4

6

8

10

12

14

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

225


0

1

2

3

4

5

6

7

8

9

10

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

226







00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

tem

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

227



00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

228


[M+H]+

[M+Na]+ [M+K]

+

229

AP

PE

ND

IX 7

- 1H N

MR

spectru

m fo

r DT

PA

-(AlaO

Me)

2

230

GSH1ESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alize

d In

tensi

ty

Water

44

944

844

6

38

9

37

6 37

437

2 28

628

628

528

4

24

924

8 24

724

624

524

4

21

1 20

920

720

5

AP

PE

ND

IX 8

- 1H N

MR

spectru

m fo

r GS

H

231

EUGSHESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alized Inte

nsity

Water

45

044

844

7

41

8

38

037

837

7

37

136

9

30

230

1

28

7 28

628

4

24

9 24

724

624

423

323

1

21

020

820

720

5

AP

PE

ND

IX 8

a - 1H N

MR

spectru

m fo

r Eu(N

O3 )

3 + G

SH

232

5




References


System





Na5DTPA


















441 Dy3+




Systems at pH 4



119

120

121

123

124

127

127

127

127

132

133

136

137

137

139

140

140

143

145

145

148

149

151

151

153

154

155

156

157

157

160

6




References



51 Ligand Synthesis











Work

References



62 Future Work

References





amp An3+

with amino acids in

TALSPEAK systems





163

166

170

173

174

175

176

176

179

183

183

184

185

186

187

190

191

192

192

198

200

201

201

201

201

201

201

202

202

7









amino acid studies


amino acid studies


acid studies



Na5DTPA


with Na5DTPA


GSH studies


amino acid studies

732 Gamma counting

733 ICP-MS


glutathione at UoM









MALDI-MS

203

203

203

205

205

205

205

205

206

206

206

206

207

207

207

208

208

208

208

209

209

210

210

210

210

8


NMR spectroscopy


7532 13

C NMR Spectroscopy


elemental analysis


ligands





76 Instruments


Co Irradiator






References

Appendices







(005 M) with Eu(NO3)3 (1 mM)





ligands


211

211

213

215

216

216

216

216

216

217

217

217

218

218

219

220

220

222

223

224

226

228

9





229

230

231

10

LIST OF TABLES








Reactors (LWR)


with amino

acidslactate




Am3+





[Eu(DTPA)]2-







system







values

Table 41 Eu3+

Am3+



11

Table 42 Eu3+

Am3+



Table 43 Eu3+

Am3+



pH 4

Table 44 Eu3+

Am3+



pH 4


with GSH at

pHD 4















in the




in the






γ-radiation

12








in the






and Tb3+

samples at pH 4




and Tb3+




HDEHP in dodecane












kGy γ-radiation



kGy γ-radiation

13


after Eu3+





phases after Eu3+





Co

irradiator at DCF



present ()


ions

14

LIST OF FIGURES


phosphorescence


Ln3+

complexes






U into 92

Kr and

141

Ba
























15













of MA3+

and Ln3+








pD = 36


a) pD 7 [DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]



in D2O

at pD 36


2- in 41 vv



and [Cm(DTPA)]2-

in




concentration






16



2- (10 mM) with L-



in D2O at pD 3 with



in





395 nm at 298 K



395 nm


in H2O with and


nm




and Am3+

in the presence of











system


Y3+


mM LnY3+





17






pH 2

Figure 37 Eu3+

Am3+



Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



Figure 310 Eu3+

Am3+




-Ho3+

and Am3+

with 05 M L-



acid (bottom)




Figure 44 Eu3+

Am3+




Figure 45 Eu3+

Am3+




Figure 46 Eu3+

Am3+



tests




18




Figure 410 Eu3+

and Am3+




and Eu3+


repeat tests

Figure 411 Eu3+

and Am3+



for Eu3+


Am3+


Figure 412 Eu3+

and Am3+




and Eu3+


from 3 repeat tests






at 397 nm



at 397 nm


Eu3+











19






extraction




extraction










Eu3+



nm


extraction





extraction







397 nm


Eu3+



of 01-06 M

20












10

mM Dy3+


for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

21




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)









Figure 442 1H


Cys (bottom)









extraction






nm




nm

22




nm





Eu3+





Am3+




Am3+




Am3+






kerosene







kerosene






Figure 75 13


Figure 76 13


23

Figure 77 13


Figure 78 13


Figure 79 60



24

ABSTRACT



PhD


Separations

2015









) components




allowing Ln3+





















Eu3+

Am3+










Eu3+

Am3+




Am3+



processes

25

DECLARATION




26

COPYRIGHT STATEMENT
























27

ACKNOWLEDGEMENTS





new experience





Adam Swinburne



all of your help





















28




work














29


gt greater than

˂ less than


percent


α alpha

β beta

γ gamma

δ chemical shift

Δ change in


λ wavelength

microL microlitres

micros microseconds

ρ density

τ lifetime

ν frequency

ν= energy level

wavenumber

Aring angstroms





au arbitrary units


hydration sphere

Bq Becquerel

cm centimetres



E energy

F Faradays constant

30

g grams


Gy Gray

h Plancks constant

Hz Hertz

J Joules


K Kelvin

kBq kiloBecquerel

kg kilograms

kGy kiloGray

kJ kiloJoules

L litres


M molar (moldm-3

)

mg milligrams

MHz megaHertz

min minute(s)

mL millilitres

mm millimetres

mM millimolar

mol moles

mmol millimoles

ms milliseconds

ng nanograms

nm nanometres

ns nanoseconds




s seconds

t time


31


An actinides

aq aqueous





Alternatives


mass spectrometry




















EC electron capture




32





FP fission products


GSH glutathione






I ionic strength





IR infra-red





Lac lactate



Ln lanthanides



M metal

MA minor actinides


spectrometry

MOX mixed oxide



33

nIR near-infra-red




org organic













TEA triethylamine













UV ultra-violet




34



Alanine Ala

Arginine Arg

Asparagine Asn

Aspartic acid Asp

Cysteine Cys

Glutamic Acid Glu

Glutamine Gln

Glycine Gly

Histidine His

Isoleucine Ile

Leucine Leu

Lysine Lys

Methionine Met

Phenylalanine Phe

Proline Pro

Serine Ser

Threonine Thr

Tryptophan Trp

Tyrosine Tyr

Valine Val

35

1 INTRODUCTION


111 Background










the early 20th

















commercially5




36












238U (n γ)

239U rarr

239Np rarr

239Pu (n γ)

240Pu (n γ)

241Pu rarr

241Am (n γ)

242mAm rarr

242Cm



processes6




ions can be














ions relatively

readily

β- β

- β

- β

-


37



Configuration

(Metal)

Electron

Configuration

(Ln3+

)

3rd

Ionisation

Energy

(kJmol-1

)

4th

Ionisation

Energy

(kJmol-1

)


2 [Xe] 1850 4819

Ce Cerium [Xe]4f15d

16s

2 [Xe]4f

1 1949 3547


2 [Xe]4f

2 2086 3761


2 [Xe]4f

3 2130 3899


2 [Xe]4f

4 2150 3970


2 [Xe]4f

5 2260 3990


2 [Xe]4f

6 2404 4110


16s

2 [Xe]4f

7 1990 4250


2 [Xe]4f

8 2114 3839


6s2 [Xe]4f

9 2200 4001

Ho Holmium [Xe]4f11

6s2 [Xe]4f

10 2204 4100

Er Erbium [Xe]4f12

6s2 [Xe]4f

11 2194 4115

Tm Thulium [Xe]4f13

6s2 [Xe]4f

12 2285 4119


6s2 [Xe]4f

13 2415 4220


5d16s

2 [Xe]4f

14 2022 4360












to

An3+

and An3+

to An2+


38


An4+





subshell of Cm3+





Config

(Metal)

Electron

Config

(An2+

)

Electron

Config

(An3+

)

Electron

Config

(An4+

)


2 NA [Rn]6d

1 [Rn]


17s

2 NA [Rn]5f

2 [Rn]5f

1

U Uranium [Rn]5f36d

17s

2 NA [Rn]5f

3 [Rn]5f

2


17s

2 NA

[Rn]5f

4 [Rn]5f

3


2 NA [Rn]5f

5 [Rn]5f

4


2 [Rn]5f

7 [Rn]5f

6 [Rn]5f

5

Cm Curium [Rn]5f76d

17s

2 NA [Rn]5f

7 [Rn]5f

6


2 NA [Rn]5f

8 [Rn]5f

7


7s2 [Rn]5f

10 [Rn]5f

9 [Rn]5f

8


7s2 [Rn]5f

11 [Rn]5f

10 [Rn]5f

9

Fm Fermium [Rn]5f12

7s2 [Rn]5f

12 [Rn]5f

11 [Rn]5f

10


7s2 [Rn]5f

13 [Rn]5f

12 [Rn]5f

11


7s2 [Rn]5f

14 [Rn]5f

13 NA


6d17s

2 NA [Rn]5f

14 NA

39



unknown8







Equation 11





Equation 12






Equation 13

7 NpO23+

PuO23+

AmO65-

6 UO22+

NpO22+

PuO22+

AmO22

+5 PaO2

+UO2

+NpO2

+PuO2

+AmO2

+

4 Th4+

Pa4+

U4+

Np4+

Pu4+

Am4+

Cm4+

Bk4+

Cf4+

3 Ac3+

Th3+

Pa3+

U3+

Np3+

Pu3+

Am3+

Cm3+

Bk3+

Cf3+

Es3+

Fm3+

Md3+

No3+

Lr3+

2 Am2+

Cf2+

Es2+

Fm2+

Md2+

No2+



40

































ions allows them

41


solution






the lanthanides












and the An3+




ion The Am7+


conditions



lanthanides

1171 Hydrolysis



and An3+






+ H3O+




AnO2+ lt An

3+ lt AnO2

2+ lt An

4+

42


position of AnO22+









ions having a






aqueous solution12









+ EDTA4-









43








The



Equation 16






Equation 17

Equation 18













44














does not



luminescent

45




spectrum




Pr3+

Sm3+

Nd3+

Eu3+

Ho3+

Tb3+

Er3+

Dy3+

Yb3+

Tm3+

Gd3+

(UV)

Ce3+

(UV)










and Th4+


has a full 4f


performed on Fm3+

Md3+

or No2+



Am3+

and Cm3+




46




spectrum



of the spectrum

NpO22+

Pa4+

(UV) Pa4+

Pa4+

Pa4+

Pa4+

Am3+

U4+

(UV) U4+

Es3+

UO2+

UO22+

UO22+

UO22+

UO22+

Am3+

Am3+

Am3+

Am3+

Cm3+

Bk3+

Cf3+
























47





complexes 1S



ion 19







(2S+1)LJ










48

1226 Quenching












) thermal




Tb3+



is very high

(20500 cm-1


Eu3+





Ho3+

Er3+

Tm3+

Yb3+

Dy3+

and Sm3+

with


has the









chromophores

49


3H4

4I132

4I112

3H4

3H5

3H6

3H6

3H5

3H4

0

20000

4I92

4I112

4I132

4I152

4F32

2H92

4S32

4F92

2H112

4G52

4G72

4G92

(2D2P)32

4G1125D4

7F07F17F27F37F4

7F5

7F67F0

7F1

7F2

7F3

7F4

7F5

7F6

5D0

5D1

5D2

2F52

2F72

10000

6H52

6H72

6H92

6H112

6H132

4F32

4G52

4F32

4F12

4F52

4F72

4G72

4F92

4F112

3F2

3F4

3P0

3P1

3F3

1I6

1G4

4I92

4F92

4S32

4F72

3F4

3F3

3F2

1G4

E

cm

-1

=0

=1

=2

=3

=4

=5

=0

=1

=2

=3

=4

=5

=6

=7

2H112

1D2







Figure 14

50













Equation 19

Equation 110





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+


51


and A = 42 for Tb3+




for Eu3+


for Tb3+

242526

13 Nuclear Theory

131 Nuclear Power








15


U into 92

Kr and 141

Ba27






52







(~2 kJ mol-1


C or 2H)










of 235

U238























53







produced




The amount of waste







54











Constituent of SNF

U 956


Pu 09

Cs amp Sr (FP) 03

I amp Tc (FP) 01


MA 01










However the




ions with ligands35


and

Cm3+

from Ln3+

55











the species36




Equation 111

Equation 112



1341 PUREX







Equation 113 UO22+


Equation 114 PuO22+


56


corresponding Pu4+


(Equation 115)





and 117)









4+ to Pu

3+ with



-


The Pu3+







The process






57


treatment40



1342 TRUEX




58
















59


1343 DIAMEX









The nitric



Oxalic acid is











60




1344 SANEX











61









bipyridine)




62


1345 i-SANEX





and Cm3+


and Ln3+

ions are









process50









been proposed51

63

1346 GANEX









over Eu3+

gt 1000







For the











bipyridine)

64




phenanthroline)

65


1347 TRPO

















66










67


1348 LUCA





from Cm3+

Cf3+

and Ln3+

after co-extraction






concentrations55




68


1349 EXAm





from Cm3+






and Ln3+

in




Cm3+

and TEDGA is





69

137 TALSPEAK






(Am3+

and Cm3+

) from

Ln3+

and yttrium (Y3+












problem

1371 The Process






for Nd3+







Without DTPA Eu3+

Am3+





70



TALSPEAK Process







separation




and

Ln3+



DTPA5-





phosphate)


HEH[ϕP] ((2-(2-


71




The Ln3+


of the DTPA5-



MA[DTPA]2-


is bound




4 After the Ln3+





rate as the DTPA5-


allowing them to be


dissociates The





separation If Ln3+

and Y3+




the raffinate



and Es3+

but it



72


DTPA to M3+


extraction of Ln3+
















1 2

73


and Ln3+


60



An3+






chemistry62

74



















75






in storage









practicality




Initial research in
















have been explored

76


















77











1966 1 6-10














2188







Chem Rev 2014 266-267 171-193




78











Great Britain 1999









2012



Compounds 2000 303-304 137-141



Cambridge UK 2011



130-134


3373-3376




79


Extr Ion Exch 1985 31 75-109





1997 47 57-67














29 190








7 349-357




377


2010 28 3 287-312

80








2892-2893





282 523-526


50 7937-7939

81






























radiotherapy7

82







of LnDTPA2-


to take place For

LnDTPA2-




complexes






- 2348 for CmDTPA2-






2219 - 2085 for CmDTPA2-






Cm3+




83

strength to DTPA5-

than Eu3+


CmDTPA2-

than EuDTPA2-

(-407 kJ mol-1

vs -336 kJ mol-1

) determined by


to DTPA5-

than Eu3+


CmDTPA2-



in D2O for Cm3+




was







to the ligand









extraction as the

MDTPA2-











LnHDTPA- species


84


to MA3+


octadentate





and EuDTPA2-




than Eu3+


Cm3+






to MHDTPA-


than Eu3+

so



3+ This data is








H2O)










85

EUDTPAESP

15 10 5 0 -5 -10 -15 -20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

152

8

99

196

6

88

4

53

7

42

536

033

528

7

15

8

-01

1

-16

1

-40

6

-57

3-6

33

-105

3

-126

8

-148

3

-170

2

-184

7


2- in D2O at 278 K at pD = 36

DTPA pH71resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

199100215418

DEUTERIUM OXIDE

Water

38

1

34

033

833

632

8

30

630

530

3

a

86

DTPA pH361resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

204206100421

Water

47

647

5

38

5

35

634

634

434

3

31

531

431

2

DTPA pH21resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

202199100406

Water

47

5 46

9

39

0

35

4

34

033

933

7

31

130

930

8


[DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]




5- (005






Eu3+




ligand to Eu3+

ion at pH 361617



to DTPA5-


b

c

87


solvent molecules



in D2O at pD 36


(aq) and the

[Eu(DTPA)]2-







Equation 21

Equation 22





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+



and A = 42 for Tb3+


0

2

4

6

8

10

12

14

16

18

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

[Eu(DTPA)]2-

Eu3+

5D0 rarr 7F0

5D0 rarr 7F1

5D0 rarr 7F2

5D0 rarr 7F3

5D0 rarr 7F4

88

0075x) ms-1


and A =

5 ms and B = 006 ms-1

for Tb3+



ion is










ions

than Ln3+



and Cm3+

complexation



and Cm3+








the 241







The Am3+



89


but in this ion




the second J




Indeed


[Am(DTPA)xH2O]2-


7F1 excited







243Cm

3+ (015 microM Cm

3+ in 32



Cm3+




8S72


3+(aq)


in Cm3+


due to more

210 K

265 K

300 K

365 K

90





and [Cm(DTPA)]2-



Similarly to Eu3+


ion is known to





Equation 23













ions27

to form

40

45

50

55

60

65

70

75

80

570 590 610 630

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

Cm3+(aq)

[Cm(DTPA)]2-

91

M3+


3+-lactate

complexes

Equation 24a-c

(a)

(b)

(c)









5D0 rarr



ion changes as a









92

mode to Ln3+





28



ion and the








over Am3+

DTPA is required to


from Ln3+


holdback reagent



and M(Lac)n3-n

Studies carried






ternary M3+








93







ions32





668


and [M(DTPA)]2-






(bottom right)



1H




94

New Eu Ala0011resp

55 50 45 40 35 30 25 20 15 10 05 0


0

005

010

015

Norm

alized Inte

nsity

310100

CH3

CH

Water

47

147

1

35

5

12

712

6


278 K

Ala1resp

55 50 45 40 35 30 25 20 15 10 05 0


0

01

02

03

04

05

06

07

08

09

10

Norm

alized Inte

nsity

336100

CH3

CH

Water

36

536

336

2

13

3


95







EuDTPA Ala1esp

15 10 5 0 -5 -10 -15 -20


0005

0010

0015

0020

0025

0030

0035

Norm

alized Inte

nsity

150

5 96

892

185

2

75

4

50

4

39

533

231

625

8

14

6

05

0

-13

1

-44

2

-63

3-6

86

-108

2

-127

6

-143

1

-169

0

-183

9



at 278 K
















96


region (Figure 214)













0

100

200

300

400

500

600

700

0

5

10

15

20

25

30

220 320 420 520 620

Ab

sorp

tio

n In

ten

sity

(au

) Th

ou

san

ds

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

TbDTPA exc 379 nm




97

















seen in Table 21

0

2

4

6

8

10

12

14

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+

Eu-Lactate

Eu-Gly

Eu-Ala

Eu-Ser

98








metal







0

5

10

15

20

25

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser


Eu3+

011 165 89


Eu Gly 016 183 60

Eu Ala 016 187 60

Eu Ser 019 147 48

99


to [Eu(DTPA)]2-








seen in Table 22


with amino



upon


the Eu3+












Eu DTPA 063 230 23





100







Cm3+

to DTPA5-


[Cm(DTPA)]2-









processes33









40

45

50

55

60

65

70

75

80

570 580 590 600 610 620 630 640

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

[Cm(DTPA)]2-

[Cm(DTPA)]2- + Ala

101











from Am3+









32 33 34 3517

18

19

20

21

Alanine (pH 30)

Lactate ion (pH 60)

Lactic acid (pH 10)

ToC k M

-1 s

-1Error

1046 59E7 49E6

306 849E7 421E6

305 832E7 419E6

402 102E8 816E6




R2 = 0990

ln (

kM

-1 s

-1)

103Temp (K)

102


and Am3+




Am3+



not defined



pH 2 5620 5519 5132 5103

pH 3 1595 1653 1589 1252


The [Eu(DTPA)]2-




103










0

50

100

150

200

250

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

0

20

40

60

80

100

120

140

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

104








[Eu(DTPA)]2-




systems before and


τ of aqueous

phase

before

irradiation

(ms)

τ of aqueous

phase

after

irradiation

(ms)

τ of

organic

phase

before

irradiation

(ms)

τ of

organic

phase

after

irradiation

(ms)

Eu DTPA 063 066 222 262


Eu DTPA Gly 065 064 247 249

Eu DTPA Ala 065 065 211 238

Eu DTPA Ser 065 062 260 251

τ of

aqueous

phase

before

irr [H2O]

(ms)

τ of

aqueous

phase

after

irr[H2O]

(ms)

τ of

aqueous

phase

before irr

[D2O] (ms)

τ of

aqueous

phase

after irr

[D2O] (ms)

q

before

irr

q after

irr

Eu DTPA 063 066 230 227 11 10

Eu DTPA

Lactate

063 063 216 210 10 10

Eu DTPA

Gly

065 064 203 208 10 10

Eu DTPA

Ala

065 065 209 211 10 10

Eu DTPA

Ser

065 062 208 206 10 10

105











and [Eu(DTPA)]2-






ion when



and Cm3+



amino acidslactate


was





or Cm3+


[Eu(DTPA)]2-





106



2788


6445





107 758-769


1999 42 15 2988ndash2992





1968 10 94

11 I Bayat KFK



2013 101 221









89





107










271273 719





14547-14556


313-334




97 9 497-502







108


ACID BUFFERS












MA3+
























3 A pH 1 system

109



comparison

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring



Y3+


1 M


110












086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring


system

111










Lactic

Acid

10 3 0009 380 140 mdash 91







ions including Ln3+

and An3+

Aziz et al67


and Am3+

at pH 36












ion with



112


















113








H7DTPA2+


3+ and Ln






Ln3+

ions is H3DTPA2-

At pH 3 a much







INL

114







115





over Am3+













phase

y = -09383x - 15277 Rsup2 = 09854

y = -11258x + 01381 Rsup2 = 09289

-10

-05

00

05

10

15

20

-125 -12 -115 -11 -105 -1 -095

log

DEu

Am

log [Na5DTPA]

Am Extraction

Eu Extraction

116

Figure 37 Eu3+

Am3+


M) at pH 2










less Am3+







y = -08451x - 14757 Rsup2 = 09936

y = -07958x + 03998 Rsup2 = 0998

-15

-10

-05

00

05

10

15

-11 -1 -09 -08 -07 -06 -05 -04 -03

log

DEu

Am

log [Na5DTPA]


117

Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



y = 13522x + 02972 Rsup2 = 09283

y = 09682x + 19794 Rsup2 = 09561

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

y = 14702x + 00193 Rsup2 = 09981

y = 11892x + 17129 Rsup2 = 09713

-10

-05

00

05

10

15

20

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

118

Figure 310 Eu3+

Am3+













[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10




y = 11522x - 00047 Rsup2 = 09867

y = 12575x + 18424 Rsup2 = 09976

-10

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

119


[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 012 053 121 126 203

03 010 027 050 077 102

04 008 036 051 077 102



















in Table 35

120













Buffer pH DAm

DEu

SF

Lactic Acid 3 0009 0819 91


2 018 1016 57


2 053 4463 84

3 007 660 99

121


-Ho3+

and Am3+


pH 2 and pH 3






higher pH




Ln3+

Am3+











001

01

1

10

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

His pH 2

His pH 3

Am pH 2

Am pH 3

122












other amino acids

123


2014 32 378-390















2010 28 3 287-312

124


SYSTEM






in an aqueous

phase allowing Ln3+







industrial process









42)

125


(bottom)


vitamin B9 (bottom)






126














Ln3+

separation












to 751

for Ho3+









127



and Eu3+



















and Am3+

Over a



temperature







128

Figure 44 Eu3+

Am3+



tests

Figure 45 Eu3+

Am3+



tests




over Am3+


-02

0

02

04

06

08

1

12

14

16

18

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

-1

-08

-06

-04

-02

0

02

04

06

08

1

12

14

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

129










Figure 46 Eu3+

Am3+









-15

-10

-05

00

05

10

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

130

Table 41 Eu3+

Am3+


Na5DTPA at pH 4













131














4 (right)10

132











Figure 410 Eu3+

and Am3+



and Eu3+

Results


y = 19018x2 - 23123x + 72258 Rsup2 = 09937

y = 0442x2 - 03543x + 00659 Rsup2 = 0781

00

00

01

01

02

-20

-10

00

10

20

30

40

50

60

70

-01 26E-15 01 02 03 04 05 06 D

Am

DEu

[Na5DTPA] (M)

Eu extraction

Am extraction

133

Table 42 Eu3+

Am3+































134

Figure 411 Eu3+

and Am3+






Table 43 Eu3+

Am3+















y = -30649x2 + 3243x + 15029 Rsup2 = 09467

y = 00013x + 00015 Rsup2 = 08028

0000

0002

0004

0006

0008

0010

0012

0014

00

05

10

15

20

25

30

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

135

Figure 412 Eu3+

and Am3+



and Eu3+


Table 44 Eu3+

Am3+

















these conditions

y = -01882x + 08847 Rsup2 = 08326

y = 17968x - 04007 Rsup2 = 09946

-0500

0000

0500

1000

1500

2000

00

01

02

03

04

05

06

07

08

09

10

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

136



















0

1

2

3

4

5

6

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+ in H2O

Eu with GSH

Eu with DTPA

137

























in each case (q)

00

01

02

03

04

05

06

07

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

138


















00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

139


with GSH at pHD 4


[GSH]

(M)


01 1487 428 17

02 785 353 16

03 829 440 11

04 1545 161 58

05 1016 168 52







extraction at



Eu3+






00

01

01

02

02

03

03

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


140


ion is extracted as


spectrum11












00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

141










00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

142



J=1J=2

[GSH] (M)

01 02 03 04 05 st dev t-test

pD 2 0335 0399 0379 0375 0361 0024 No sig diff

pD 3 0440 0433 0451 0439 0419 0012 No sig diff

pD 4 0438 0467 0413 0469 0454 0023 No sig diff

st dev 0060 0034 0036 0048 0047

















143




pH 2 01 1699 plusmn 7 607 plusmn 9 10

pH 2 02 1692 plusmn 10 619 plusmn 10 09

pH 2 03 1686 plusmn 9 629 plusmn 9 09

pH 2 04 1636 plusmn 12 607 plusmn 13 09

pH 2 05 1596 plusmn 11 629 plusmn 13 09

pH 3 01 1755 plusmn 14 626 plusmn 7 09

pH 3 02 1737 plusmn 13 626 plusmn 15 09

pH 3 03 1723 plusmn 5 626 plusmn 13 09

pH 3 04 1720 plusmn 14 635 plusmn 17 09

pH 3 05 1677 plusmn 9 641 plusmn 14 09

pH 4 01 1778 plusmn 14 593 plusmn 16 10

pH 4 02 1747 plusmn 13 640 plusmn 15 09

pH 4 03 1679 plusmn 15 669 plusmn 18 08

pH 4 04 1689 plusmn 14 623 plusmn 15 09

pH 4 05 1679 plusmn 13 652 plusmn 19 08



complex The




GSH with the Eu3+







144















00

05

10

15

20

25

30

35

40

45

50

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Aq

03 M GSH pH 4 Aq

05 M GSH pH 4 Aq

05 M GSH pH 3 Aq

05 M GSH pH 2 Aq

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Org

03 M GSH pH 4 Org

05 M GSH pH 4 Org

05 M GSH pH 3 Org

05 M GSH pH 2 Org

145





as the HDEHPDEHP



ions GSH is




varied

J=1J=2

[GSH] (M)


pD 4 0202 0276 0247 0037 No sig diff

pD 3 - - 0100 - -

pD 2 - - 0500 - -

st dev - - 0202

t-test - - Sig diff







146










0

5

10

15

20

25

30

35

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

0

2

4

6

8

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

147



J=1J=2

[Na5DTPA] (M)

005 01 02 03 04 05 06 stdev t-test

D2O 0437 0441 0431 0437 0428 0425 0403 0013

No sig

diff

H2O 0450 0440 0437 0449 0422 0424 0428 0011

No sig

diff


















with GSH

148



[Na5DTPA]

(M)


005 1679 plusmn 3 652 plusmn 2 08

01 1549 plusmn 4 659 plusmn 2 10

02 1348 plusmn 4 666 plusmn 3 09

03 1179 plusmn 4 665 plusmn 3 08

04 1076 plusmn 4 674 plusmn 4 07

05 978 plusmn 4 698 plusmn 4 05

06 916 plusmn 5 714 plusmn 5 03






extraction with



0

1

2

3

4

5

6

7

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

149








phase





J=1J=2 0552 0578 0502 0039 No sig

diff






and 426

150














J=1J=2 0472 0499 0455 0510 0025 No sig

diff

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Aq

06 M HDEHP Aq

08 M HDEHP Aq

10 M HDEHP Aq

151





The lowest Eu3+



concentrations Am3+








Facility using a 60



seen in Figure 427

00

00

00

01

01

01

01

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Org

06 M HDEHP Org

08 M HDEHP Org

10 M HDEHP Org

152











00

01

01

02

02

03

03

04

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

153




[Na5DTPA] (M)

01 02 03 04 05 06 st

dev

t-test

J=1J=2 0477 0481 0452 0401 0407 0411 0036

No sig

diff



kGy γ-radiation


01 648 plusmn 4 1895 plusmn 12 10

02 661 plusmn 6 1678 plusmn 10 09

03 670 plusmn 6 1536 plusmn 11 08

04 679 plusmn 5 1462 plusmn 9 07

05 701 plusmn 7 1328 plusmn 10 05

06 696 plusmn 6 1211 plusmn 8 03






154


extraction from


range of 01-06 M















J=1J=2 0505 0563 0551 0031 No sig diff



under a variety



0

1

2

3

4

5

6

7

8

9

10

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Hu

nd

red

s

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

155



Also like Eu3+



441 Dy3+







is relatively








6H152 and

7F92 rarr







00

02

04

06

08

10

12

14

16

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O

Dy DTPA

Dy GSH

7F92 rarr

6H152

7F92 rarr

6H132

156







352 nm









lanthanides







00

02

04

06

08

10

12

14

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O Aq

Dy DTPA Aq

Dy GSH Aq

Dy H2O Org

Dy DTPA Org

Dy GSH Org

157



excitation







Systems at pH 4

The Dy3+



Eu3+

Tb3+

and Dy3+




irradiation





data

00

01

02

03

04

05

06

07

08

09

10

550 560 570 580 590

Emis

sio

n In

ten

sity

(au

) x 1

00

00

Wavelength (nm)

pH 2 Aq

pH 3 Aq

pH 4 Aq

pH 4 (03 M DTPA) Aq

pH 2 Org

pH 3 Org

pH 4 Org


158


10 mM Dy3+

) in H2O


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10 mM Dy3+

) with


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

0

5

10

15

20

25

30

35

40

45

50

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

0

2

4

6

8

10

12

14

16

18

20

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

159


10 mM Dy3+

005 M


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)








complex can also be

seen for the Tb3+



or Dy3+




Ln3+


Ln3+

with

GSH



0

1

2

3

4

5

6

7

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

160





and Tb3+

as calculations of

q for Sm3+

and Dy3+




ion with




and Tb3+

samples at pH 4


Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

Ln3+


Ln3+

with

GSH











and Tb3+

are as



161


10 mM Dy3+

) with


397

nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


pH range of 2-4







and Tb3+

samples before



Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)




00

10

20

30

40

50

60

70

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

162





with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

163


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)







and Dy3+



and Eu3+





the Ln3+



Ln3+


MS






00

05

10

15

20

25

30

35

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

164







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

0

5

10

15

20

25

30

35

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

165

















166



pH

[GSH]

(M)

SF


2 01 234 171 148 107 136 158 216 222 237 234

2 02 244 176 145 103 134 146 215 229 239 244

2 03 263 183 145 105 137 165 243 244 281 289

2 04 239 170 151 111 145 168 218 237 259 265

2 05 278 197 164 117 162 189 257 269 300 314

3 01 1735 972 477 276 163 104 112 53 41 38

3 02 1953 841 433 256 320 266 290 130 89 77

3 03 1898 785 388 220 152 90 95 39 28 24

3 04 2046 812 412 243 196 121 126 53 38 34

3 05 2145 705 312 139 36 16 20 04 02 00

4 01 3777 141 12 - - - - - - -

4 02 5548 231 36 06 - - - - - -

4 03 2768 239 27 - - - - - - -

4 04 1620 150 21 01 - - - - - -

4 05 1589 286 48 11 - - - - - -







167

GSH0011resp

45 40 35 30 25 20 15 10


0

005

010

Norm

alized Inte

nsity

197201200100200099

c

d

gb

i

f

44

944

844

6

38

9

37

637

437

2

28

628

628

528

4

24

924

824

724

624

524

4

21

120

920

720

5


45 40 35 30 25 20 15 10


0

005

010

015

020

025

Norm

alized Inte

nsity

133151244272014101206498131111059100

m

c

d

n

g

q

b

l

i

p

f

47

0

44

7 44

544

442

942

841

641

541

140

940

940

738

137

737

537

3

36

736

6

29

929

728

428

328

1

26

7

24

6

24

424

324

223

823

022

822

6

20

720

520

419

6

19

519

419

319

1

a

b

168

Eu GSH0011resp

45 40 35 30 25 20 15 10


005

010

015

Norm

alized Inte

nsity

035183050206177050088216024026100

d

g

b

i

f

c

45

044

844

7

42

0 41

841

741

341

241

138

0 37

837

737

136

9 30

230

1

28

928

728

628

428

328

1

25

124

924

724

624

424

2 23

3 23

122

921

020

820

720

519

919

819

719

6

GSH DTPA0011resp

45 40 35 30 25 20 15 10


0

005

010

015

Norm

alized Inte

nsity

032158045179156092075366021025099

c

d

g

DTPA

DTPA

DTPA

b

DTPA

i

f

45

044

9 44

744

6

41

941

841

741

241

141

0

37

937

737

537

036

8

34

133

633

5

30

730

530

1

28

928

628

528

428

228

0

25

024

824

624

524

324

1 23

223

022

821

020

820

620

419

719

5

c

d

169

EuDTPA GSH0011resp

45 40 35 30 25 20 15 10


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

180181200200212103673021100

47

0

44

244

1

38

4

36

836

3

32

832

0 30

230

129

9 28

628

528

328

1

24

724

624

524

424

3

20

820

720

520

3




Figure 442 1H





e

170













422)









and Am3+

when used without

Na5DTPA





Eu3+

and Am3+





experiments






171


extraction























with pH







conditions






172





irradiation











Dy3+




decreasing as


for Tb3+

and Dy3+


and Eu3+













173

















Chem B 2012 116 46 13722-13730


Chem 2010 8 4915-4920



174











) ions


by HDEHP (di-



considered






the MA3+



over Ln3+

This is













INE

175





















Protected

Protected Protected

176













0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

177






Eu3+




centre as expected


complexes at pD 2-4

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

0

5

10

15

20

25

30

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

178

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pD 2 0359 0381 0404 0353 0023

No sig

diff

pD 3 0394 0425 0417 0381 0020

No sig

diff

pD 4 0391 0427 0432 0423 0019

No sig

diff

st dev 0019 0026 0014 0035

t-test No sig

diff

No sig

diff

No sig

diff

No sig

diff












179



excitation

















itself








180




at 397 nm


extraction from



0

0

0

0

0

1

1

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

0

10

20

30

40

50

60

70

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


181


extraction from




extraction from



0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


0

1

2

3

4

5

6

7

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

Ala-DTPA Org

Arg-DTPA Org

His-DTPA Org

Ser-DTPA Org

182























Eu3+


pH 2-4

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pH 2 0208 0207 0198 0208 0005 No sig diff

pH 3 0210 0213 0311 0347 0069 Sig diff

pH 4 0182 0210 0206 0205 0013 No sig diff

st dev 0016 0003 0063 0081


183












397 nm





0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

184



DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-


J=1J=2 0357 0395 0412 0362 0026 No sig

diff













extraction from



0

1

2

3

4

5

6

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


185












DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

J=1J=2 0241 0233 0198 0231 0019

No sig

diff





without irradiation

(micros)


irradiation









186



Am + 152

Eu (1 kBq mL-1






and Eu3+








and Eu3+

for these











Am3+

using DTPA-


187


Am3+

using DTPA-



Am3+

using DTPA-




Am3+





and Am3+

can be seen in


Am3+

(as

188

Nd3+









189







190






complex to Eu3+





over Am3+





with the ligands








between Ln3+

Am3+






Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30








191






192





and MA3+




allowing Ln3+












from Ln3+

23









Ln3+




Am3+

is achieved








organic phase

193


keeping Am3+

















lanthanides



and [Eu(DTPA)]2-






Eu3+




ion when



and Cm3+





or Cm3+




194







and the



operation








and Am3+

when used without

Na5DTPA






Eu3+

and Am3+




the pH is increased







Am3+


TALSPEAK process



195

































can occur Further




Eu3+

Tb3+

and Dy3+






196




and Dy3+

which are


and Eu3+



-Ho3+






acid systems



Eu3+

Am3+









MA3+







at pH 2 3 and 4











irradiation



between Ln3+

Am3+


197





Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30



















the use of amino







with lactate15


Cm3+

with DTPA16


with





however there are



198

62 Future Work
















199




















and Cm3+














ratio of Am3+





200




10 245-279



523-526






2014 32 378-390





47 8856



2012 65 16 2862-2876











amino-acidshtm 2015




201
























were returned


amp An3+









202






Stock solutions




0625 M L-Phe in D2O







1 M amino








Equation 71









203







such as from a 60




H2O rarr H + OH

OH + Fe2+

rarr Fe3+

+ HO-

H + O2 rarr HO2

H+ + Fe

2+ + HO2 rarr Fe

3+ + H2O2

H2O2 + Fe2+

rarr Fe(OH)2+

+ OH

HO2 + Fe3+

rarr Fe2+

+ O2 + H+


ions to Fe3+

The amount

of Fe3+





out using the 60










72)2

204

Equation 72

Where


-1


cm-1









For γ-rays

εFe(III) = 2197 M-1

cm-1


Equation 73

Equation 74





205




min-1

)

1 1084678

2 1171864

3 1183066

4 1103841


INL









Stock solutions

1 M Na5DTPA in H2O

1 M L-Ala in H2O














206




















Stock solutions

1 M Na5DTPA in H2O











207






















732 Gamma counting










microL 241

Am or 154



208






Am or 154


) were also



733 ICP-MS




of each of La
























209

Stock solutions
























performed at INL







210


















(145 g 6 mmol)

Yields


)


)


)


)





[M+Na]+ and [M+K]






found in Appendix 6

211


+ 603 (39) [M+K]

+


+ 772 (9) [M+K]

+


+ 662 (15) [M+K]

+


+ 735 (10) [M+K]

+







spectra 13




1H









3JHH =100 Hz 4 H


4 H H2) 375 - 387 (m 4 H H3) 418 - 425 (m 2 H H1)


3JHH 730 Hz 4 H H9) 169 - 189


365 (s 6 H H7) 368 (s 2 H H6) 375 - 384 (m 4 H H3) 436 - 444 (m 2 H H1)



Hz 4 H H8) 452 (dd 3JHH =479 378 Hz 2 H H1)


(s 4 H H3) 358 (s 6 H H7) 362 (m 2 H H6) 370 - 375 (m 1 H H3) 464 - 466

(m 2 H H1) 714 (s 2 H H9) 843 (s 2 H H10)

212




213


7532 13

C NMR Spectroscopy




1718 (q-C C11) 1721 (q-C C10) 1746 (q-C C8)




C10) 1735 (q-C C8)



1693 (q-C C9) 1712 (q-C C10) 1717 (q-c C11) 1723 (CH3 C8)



1286 (q-C C13) 1333 (CH C15) 1711 (q-C C9) 1714 (q-C C11) 1716 (q-C

C10) 1746 (q-C C8)

214

Figure 75 13


Figure 76 13


Figure 77 13


215

Figure 78 13










C () H () N () Cl () Na ()


DTPA-(AlaOMe)2

4689 4224 662 685 1243 1146 0 475 0 0

DTPA-(ArgOMe)2

4583 3896 701 637 2100 1643 0 1427 0 0

DTPA-(SerOEt)2

4622 4300 663 755 1123 1041 0 240 0 0

DTPA-(HisOMe)2

4834 3985 594 668 1812 1458 0 595 0 0

216






Stock solutions



















using the 60






217

76 Instruments


Co Irradiator


Co



Co to 60







Figure 79 60













218


ions






20 minutes




400





Ln3+


Eu 617 395

Tb 545 379

Sm 600 403

Dy 575 352

219






220

APPENDICES








00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

221




00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

222







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

0

50

100

150

200

250

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

223


(1 mM)


mM)


DTPA-(AlaOMe)2 243

DTPA-(ArgOMe)2 238

DTPA-(SerOEt)2 240

DTPA-(HisOMe)2 286

224




0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

0

2

4

6

8

10

12

14

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

225


0

1

2

3

4

5

6

7

8

9

10

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

226







00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

tem

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

227



00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

228


[M+H]+

[M+Na]+ [M+K]

+

229

AP

PE

ND

IX 7

- 1H N

MR

spectru

m fo

r DT

PA

-(AlaO

Me)

2

230

GSH1ESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alize

d In

tensi

ty

Water

44

944

844

6

38

9

37

6 37

437

2 28

628

628

528

4

24

924

8 24

724

624

524

4

21

1 20

920

720

5

AP

PE

ND

IX 8

- 1H N

MR

spectru

m fo

r GS

H

231

EUGSHESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alized Inte

nsity

Water

45

044

844

7

41

8

38

037

837

7

37

136

9

30

230

1

28

7 28

628

4

24

9 24

724

624

423

323

1

21

020

820

720

5

AP

PE

ND

IX 8

a - 1H N

MR

spectru

m fo

r Eu(N

O3 )

3 + G

SH

232

6




References



51 Ligand Synthesis











Work

References



62 Future Work

References





amp An3+

with amino acids in

TALSPEAK systems





163

166

170

173

174

175

176

176

179

183

183

184

185

186

187

190

191

192

192

198

200

201

201

201

201

201

201

202

202

7









amino acid studies


amino acid studies


acid studies



Na5DTPA


with Na5DTPA


GSH studies


amino acid studies

732 Gamma counting

733 ICP-MS


glutathione at UoM









MALDI-MS

203

203

203

205

205

205

205

205

206

206

206

206

207

207

207

208

208

208

208

209

209

210

210

210

210

8


NMR spectroscopy


7532 13

C NMR Spectroscopy


elemental analysis


ligands





76 Instruments


Co Irradiator






References

Appendices







(005 M) with Eu(NO3)3 (1 mM)





ligands


211

211

213

215

216

216

216

216

216

217

217

217

218

218

219

220

220

222

223

224

226

228

9





229

230

231

10

LIST OF TABLES








Reactors (LWR)


with amino

acidslactate




Am3+





[Eu(DTPA)]2-







system







values

Table 41 Eu3+

Am3+



11

Table 42 Eu3+

Am3+



Table 43 Eu3+

Am3+



pH 4

Table 44 Eu3+

Am3+



pH 4


with GSH at

pHD 4















in the




in the






γ-radiation

12








in the






and Tb3+

samples at pH 4




and Tb3+




HDEHP in dodecane












kGy γ-radiation



kGy γ-radiation

13


after Eu3+





phases after Eu3+





Co

irradiator at DCF



present ()


ions

14

LIST OF FIGURES


phosphorescence


Ln3+

complexes






U into 92

Kr and

141

Ba
























15













of MA3+

and Ln3+








pD = 36


a) pD 7 [DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]



in D2O

at pD 36


2- in 41 vv



and [Cm(DTPA)]2-

in




concentration






16



2- (10 mM) with L-



in D2O at pD 3 with



in





395 nm at 298 K



395 nm


in H2O with and


nm




and Am3+

in the presence of











system


Y3+


mM LnY3+





17






pH 2

Figure 37 Eu3+

Am3+



Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



Figure 310 Eu3+

Am3+




-Ho3+

and Am3+

with 05 M L-



acid (bottom)




Figure 44 Eu3+

Am3+




Figure 45 Eu3+

Am3+




Figure 46 Eu3+

Am3+



tests




18




Figure 410 Eu3+

and Am3+




and Eu3+


repeat tests

Figure 411 Eu3+

and Am3+



for Eu3+


Am3+


Figure 412 Eu3+

and Am3+




and Eu3+


from 3 repeat tests






at 397 nm



at 397 nm


Eu3+











19






extraction




extraction










Eu3+



nm


extraction





extraction







397 nm


Eu3+



of 01-06 M

20












10

mM Dy3+


for Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10

mM Dy3+



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)

21




Sm3+

397 nm for Eu3+

366 nm for Tb3+

and 352 nm for

Dy3+

)









Figure 442 1H


Cys (bottom)









extraction






nm




nm

22




nm





Eu3+





Am3+




Am3+




Am3+






kerosene







kerosene






Figure 75 13


Figure 76 13


23

Figure 77 13


Figure 78 13


Figure 79 60



24

ABSTRACT



PhD


Separations

2015









) components




allowing Ln3+





















Eu3+

Am3+










Eu3+

Am3+




Am3+



processes

25

DECLARATION




26

COPYRIGHT STATEMENT
























27

ACKNOWLEDGEMENTS





new experience





Adam Swinburne



all of your help





















28




work














29


gt greater than

˂ less than


percent


α alpha

β beta

γ gamma

δ chemical shift

Δ change in


λ wavelength

microL microlitres

micros microseconds

ρ density

τ lifetime

ν frequency

ν= energy level

wavenumber

Aring angstroms





au arbitrary units


hydration sphere

Bq Becquerel

cm centimetres



E energy

F Faradays constant

30

g grams


Gy Gray

h Plancks constant

Hz Hertz

J Joules


K Kelvin

kBq kiloBecquerel

kg kilograms

kGy kiloGray

kJ kiloJoules

L litres


M molar (moldm-3

)

mg milligrams

MHz megaHertz

min minute(s)

mL millilitres

mm millimetres

mM millimolar

mol moles

mmol millimoles

ms milliseconds

ng nanograms

nm nanometres

ns nanoseconds




s seconds

t time


31


An actinides

aq aqueous





Alternatives


mass spectrometry




















EC electron capture




32





FP fission products


GSH glutathione






I ionic strength





IR infra-red





Lac lactate



Ln lanthanides



M metal

MA minor actinides


spectrometry

MOX mixed oxide



33

nIR near-infra-red




org organic













TEA triethylamine













UV ultra-violet




34



Alanine Ala

Arginine Arg

Asparagine Asn

Aspartic acid Asp

Cysteine Cys

Glutamic Acid Glu

Glutamine Gln

Glycine Gly

Histidine His

Isoleucine Ile

Leucine Leu

Lysine Lys

Methionine Met

Phenylalanine Phe

Proline Pro

Serine Ser

Threonine Thr

Tryptophan Trp

Tyrosine Tyr

Valine Val

35

1 INTRODUCTION


111 Background










the early 20th

















commercially5




36












238U (n γ)

239U rarr

239Np rarr

239Pu (n γ)

240Pu (n γ)

241Pu rarr

241Am (n γ)

242mAm rarr

242Cm



processes6




ions can be














ions relatively

readily

β- β

- β

- β

-


37



Configuration

(Metal)

Electron

Configuration

(Ln3+

)

3rd

Ionisation

Energy

(kJmol-1

)

4th

Ionisation

Energy

(kJmol-1

)


2 [Xe] 1850 4819

Ce Cerium [Xe]4f15d

16s

2 [Xe]4f

1 1949 3547


2 [Xe]4f

2 2086 3761


2 [Xe]4f

3 2130 3899


2 [Xe]4f

4 2150 3970


2 [Xe]4f

5 2260 3990


2 [Xe]4f

6 2404 4110


16s

2 [Xe]4f

7 1990 4250


2 [Xe]4f

8 2114 3839


6s2 [Xe]4f

9 2200 4001

Ho Holmium [Xe]4f11

6s2 [Xe]4f

10 2204 4100

Er Erbium [Xe]4f12

6s2 [Xe]4f

11 2194 4115

Tm Thulium [Xe]4f13

6s2 [Xe]4f

12 2285 4119


6s2 [Xe]4f

13 2415 4220


5d16s

2 [Xe]4f

14 2022 4360












to

An3+

and An3+

to An2+


38


An4+





subshell of Cm3+





Config

(Metal)

Electron

Config

(An2+

)

Electron

Config

(An3+

)

Electron

Config

(An4+

)


2 NA [Rn]6d

1 [Rn]


17s

2 NA [Rn]5f

2 [Rn]5f

1

U Uranium [Rn]5f36d

17s

2 NA [Rn]5f

3 [Rn]5f

2


17s

2 NA

[Rn]5f

4 [Rn]5f

3


2 NA [Rn]5f

5 [Rn]5f

4


2 [Rn]5f

7 [Rn]5f

6 [Rn]5f

5

Cm Curium [Rn]5f76d

17s

2 NA [Rn]5f

7 [Rn]5f

6


2 NA [Rn]5f

8 [Rn]5f

7


7s2 [Rn]5f

10 [Rn]5f

9 [Rn]5f

8


7s2 [Rn]5f

11 [Rn]5f

10 [Rn]5f

9

Fm Fermium [Rn]5f12

7s2 [Rn]5f

12 [Rn]5f

11 [Rn]5f

10


7s2 [Rn]5f

13 [Rn]5f

12 [Rn]5f

11


7s2 [Rn]5f

14 [Rn]5f

13 NA


6d17s

2 NA [Rn]5f

14 NA

39



unknown8







Equation 11





Equation 12






Equation 13

7 NpO23+

PuO23+

AmO65-

6 UO22+

NpO22+

PuO22+

AmO22

+5 PaO2

+UO2

+NpO2

+PuO2

+AmO2

+

4 Th4+

Pa4+

U4+

Np4+

Pu4+

Am4+

Cm4+

Bk4+

Cf4+

3 Ac3+

Th3+

Pa3+

U3+

Np3+

Pu3+

Am3+

Cm3+

Bk3+

Cf3+

Es3+

Fm3+

Md3+

No3+

Lr3+

2 Am2+

Cf2+

Es2+

Fm2+

Md2+

No2+



40

































ions allows them

41


solution






the lanthanides












and the An3+




ion The Am7+


conditions



lanthanides

1171 Hydrolysis



and An3+






+ H3O+




AnO2+ lt An

3+ lt AnO2

2+ lt An

4+

42


position of AnO22+









ions having a






aqueous solution12









+ EDTA4-









43








The



Equation 16






Equation 17

Equation 18













44














does not



luminescent

45




spectrum




Pr3+

Sm3+

Nd3+

Eu3+

Ho3+

Tb3+

Er3+

Dy3+

Yb3+

Tm3+

Gd3+

(UV)

Ce3+

(UV)










and Th4+


has a full 4f


performed on Fm3+

Md3+

or No2+



Am3+

and Cm3+




46




spectrum



of the spectrum

NpO22+

Pa4+

(UV) Pa4+

Pa4+

Pa4+

Pa4+

Am3+

U4+

(UV) U4+

Es3+

UO2+

UO22+

UO22+

UO22+

UO22+

Am3+

Am3+

Am3+

Am3+

Cm3+

Bk3+

Cf3+
























47





complexes 1S



ion 19







(2S+1)LJ










48

1226 Quenching












) thermal




Tb3+



is very high

(20500 cm-1


Eu3+





Ho3+

Er3+

Tm3+

Yb3+

Dy3+

and Sm3+

with


has the









chromophores

49


3H4

4I132

4I112

3H4

3H5

3H6

3H6

3H5

3H4

0

20000

4I92

4I112

4I132

4I152

4F32

2H92

4S32

4F92

2H112

4G52

4G72

4G92

(2D2P)32

4G1125D4

7F07F17F27F37F4

7F5

7F67F0

7F1

7F2

7F3

7F4

7F5

7F6

5D0

5D1

5D2

2F52

2F72

10000

6H52

6H72

6H92

6H112

6H132

4F32

4G52

4F32

4F12

4F52

4F72

4G72

4F92

4F112

3F2

3F4

3P0

3P1

3F3

1I6

1G4

4I92

4F92

4S32

4F72

3F4

3F3

3F2

1G4

E

cm

-1

=0

=1

=2

=3

=4

=5

=0

=1

=2

=3

=4

=5

=6

=7

2H112

1D2







Figure 14

50













Equation 19

Equation 110





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+


51


and A = 42 for Tb3+




for Eu3+


for Tb3+

242526

13 Nuclear Theory

131 Nuclear Power








15


U into 92

Kr and 141

Ba27






52







(~2 kJ mol-1


C or 2H)










of 235

U238























53







produced




The amount of waste







54











Constituent of SNF

U 956


Pu 09

Cs amp Sr (FP) 03

I amp Tc (FP) 01


MA 01










However the




ions with ligands35


and

Cm3+

from Ln3+

55











the species36




Equation 111

Equation 112



1341 PUREX







Equation 113 UO22+


Equation 114 PuO22+


56


corresponding Pu4+


(Equation 115)





and 117)









4+ to Pu

3+ with



-


The Pu3+







The process






57


treatment40



1342 TRUEX




58
















59


1343 DIAMEX









The nitric



Oxalic acid is











60




1344 SANEX











61









bipyridine)




62


1345 i-SANEX





and Cm3+


and Ln3+

ions are









process50









been proposed51

63

1346 GANEX









over Eu3+

gt 1000







For the











bipyridine)

64




phenanthroline)

65


1347 TRPO

















66










67


1348 LUCA





from Cm3+

Cf3+

and Ln3+

after co-extraction






concentrations55




68


1349 EXAm





from Cm3+






and Ln3+

in




Cm3+

and TEDGA is





69

137 TALSPEAK






(Am3+

and Cm3+

) from

Ln3+

and yttrium (Y3+












problem

1371 The Process






for Nd3+







Without DTPA Eu3+

Am3+





70



TALSPEAK Process







separation




and

Ln3+



DTPA5-





phosphate)


HEH[ϕP] ((2-(2-


71




The Ln3+


of the DTPA5-



MA[DTPA]2-


is bound




4 After the Ln3+





rate as the DTPA5-


allowing them to be


dissociates The





separation If Ln3+

and Y3+




the raffinate



and Es3+

but it



72


DTPA to M3+


extraction of Ln3+
















1 2

73


and Ln3+


60



An3+






chemistry62

74



















75






in storage









practicality




Initial research in
















have been explored

76


















77











1966 1 6-10














2188







Chem Rev 2014 266-267 171-193




78











Great Britain 1999









2012



Compounds 2000 303-304 137-141



Cambridge UK 2011



130-134


3373-3376




79


Extr Ion Exch 1985 31 75-109





1997 47 57-67














29 190








7 349-357




377


2010 28 3 287-312

80








2892-2893





282 523-526


50 7937-7939

81






























radiotherapy7

82







of LnDTPA2-


to take place For

LnDTPA2-




complexes






- 2348 for CmDTPA2-






2219 - 2085 for CmDTPA2-






Cm3+




83

strength to DTPA5-

than Eu3+


CmDTPA2-

than EuDTPA2-

(-407 kJ mol-1

vs -336 kJ mol-1

) determined by


to DTPA5-

than Eu3+


CmDTPA2-



in D2O for Cm3+




was







to the ligand









extraction as the

MDTPA2-











LnHDTPA- species


84


to MA3+


octadentate





and EuDTPA2-




than Eu3+


Cm3+






to MHDTPA-


than Eu3+

so



3+ This data is








H2O)










85

EUDTPAESP

15 10 5 0 -5 -10 -15 -20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

152

8

99

196

6

88

4

53

7

42

536

033

528

7

15

8

-01

1

-16

1

-40

6

-57

3-6

33

-105

3

-126

8

-148

3

-170

2

-184

7


2- in D2O at 278 K at pD = 36

DTPA pH71resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

199100215418

DEUTERIUM OXIDE

Water

38

1

34

033

833

632

8

30

630

530

3

a

86

DTPA pH361resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

204206100421

Water

47

647

5

38

5

35

634

634

434

3

31

531

431

2

DTPA pH21resp

55 50 45 40 35 30 25 20


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

0060

Norm

alized Inte

nsity

202199100406

Water

47

5 46

9

39

0

35

4

34

033

933

7

31

130

930

8


[DTPA]5-

b) pD 36 [H3DTPA]2-

c) pD 2 [H5DTPA]




5- (005






Eu3+




ligand to Eu3+

ion at pH 361617



to DTPA5-


b

c

87


solvent molecules



in D2O at pD 36


(aq) and the

[Eu(DTPA)]2-







Equation 21

Equation 22





Eu3+

Tb3+

Nd3+

Yb3+

Am3+

and Cm3+



and A = 42 for Tb3+


0

2

4

6

8

10

12

14

16

18

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

[Eu(DTPA)]2-

Eu3+

5D0 rarr 7F0

5D0 rarr 7F1

5D0 rarr 7F2

5D0 rarr 7F3

5D0 rarr 7F4

88

0075x) ms-1


and A =

5 ms and B = 006 ms-1

for Tb3+



ion is










ions

than Ln3+



and Cm3+

complexation



and Cm3+








the 241







The Am3+



89


but in this ion




the second J




Indeed


[Am(DTPA)xH2O]2-


7F1 excited







243Cm

3+ (015 microM Cm

3+ in 32



Cm3+




8S72


3+(aq)


in Cm3+


due to more

210 K

265 K

300 K

365 K

90





and [Cm(DTPA)]2-



Similarly to Eu3+


ion is known to





Equation 23













ions27

to form

40

45

50

55

60

65

70

75

80

570 590 610 630

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

Cm3+(aq)

[Cm(DTPA)]2-

91

M3+


3+-lactate

complexes

Equation 24a-c

(a)

(b)

(c)









5D0 rarr



ion changes as a









92

mode to Ln3+





28



ion and the








over Am3+

DTPA is required to


from Ln3+


holdback reagent



and M(Lac)n3-n

Studies carried






ternary M3+








93







ions32





668


and [M(DTPA)]2-






(bottom right)



1H




94

New Eu Ala0011resp

55 50 45 40 35 30 25 20 15 10 05 0


0

005

010

015

Norm

alized Inte

nsity

310100

CH3

CH

Water

47

147

1

35

5

12

712

6


278 K

Ala1resp

55 50 45 40 35 30 25 20 15 10 05 0


0

01

02

03

04

05

06

07

08

09

10

Norm

alized Inte

nsity

336100

CH3

CH

Water

36

536

336

2

13

3


95







EuDTPA Ala1esp

15 10 5 0 -5 -10 -15 -20


0005

0010

0015

0020

0025

0030

0035

Norm

alized Inte

nsity

150

5 96

892

185

2

75

4

50

4

39

533

231

625

8

14

6

05

0

-13

1

-44

2

-63

3-6

86

-108

2

-127

6

-143

1

-169

0

-183

9



at 278 K
















96


region (Figure 214)













0

100

200

300

400

500

600

700

0

5

10

15

20

25

30

220 320 420 520 620

Ab

sorp

tio

n In

ten

sity

(au

) Th

ou

san

ds

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

TbDTPA exc 379 nm




97

















seen in Table 21

0

2

4

6

8

10

12

14

550 570 590 610 630 650 670 690 710

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+

Eu-Lactate

Eu-Gly

Eu-Ala

Eu-Ser

98








metal







0

5

10

15

20

25

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser


Eu3+

011 165 89


Eu Gly 016 183 60

Eu Ala 016 187 60

Eu Ser 019 147 48

99


to [Eu(DTPA)]2-








seen in Table 22


with amino



upon


the Eu3+












Eu DTPA 063 230 23





100







Cm3+

to DTPA5-


[Cm(DTPA)]2-









processes33









40

45

50

55

60

65

70

75

80

570 580 590 600 610 620 630 640

Emis

sio

n In

ten

sity

(au

) Tho

usa

nd

s

Wavelength (nm)

[Cm(DTPA)]2-

[Cm(DTPA)]2- + Ala

101











from Am3+









32 33 34 3517

18

19

20

21

Alanine (pH 30)

Lactate ion (pH 60)

Lactic acid (pH 10)

ToC k M

-1 s

-1Error

1046 59E7 49E6

306 849E7 421E6

305 832E7 419E6

402 102E8 816E6




R2 = 0990

ln (

kM

-1 s

-1)

103Temp (K)

102


and Am3+




Am3+



not defined



pH 2 5620 5519 5132 5103

pH 3 1595 1653 1589 1252


The [Eu(DTPA)]2-




103










0

50

100

150

200

250

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

0

20

40

60

80

100

120

140

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

EuDTPA

EuDTPA-Lactate

EuDTPA-Gly

EuDTPA-Ala

EuDTPA-Ser

104








[Eu(DTPA)]2-




systems before and


τ of aqueous

phase

before

irradiation

(ms)

τ of aqueous

phase

after

irradiation

(ms)

τ of

organic

phase

before

irradiation

(ms)

τ of

organic

phase

after

irradiation

(ms)

Eu DTPA 063 066 222 262


Eu DTPA Gly 065 064 247 249

Eu DTPA Ala 065 065 211 238

Eu DTPA Ser 065 062 260 251

τ of

aqueous

phase

before

irr [H2O]

(ms)

τ of

aqueous

phase

after

irr[H2O]

(ms)

τ of

aqueous

phase

before irr

[D2O] (ms)

τ of

aqueous

phase

after irr

[D2O] (ms)

q

before

irr

q after

irr

Eu DTPA 063 066 230 227 11 10

Eu DTPA

Lactate

063 063 216 210 10 10

Eu DTPA

Gly

065 064 203 208 10 10

Eu DTPA

Ala

065 065 209 211 10 10

Eu DTPA

Ser

065 062 208 206 10 10

105











and [Eu(DTPA)]2-






ion when



and Cm3+



amino acidslactate


was





or Cm3+


[Eu(DTPA)]2-





106



2788


6445





107 758-769


1999 42 15 2988ndash2992





1968 10 94

11 I Bayat KFK



2013 101 221









89





107










271273 719





14547-14556


313-334




97 9 497-502







108


ACID BUFFERS












MA3+
























3 A pH 1 system

109



comparison

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring



Y3+


1 M


110












086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

086 088 09 092 094 096 098 1

10-2

10-1

100

101

102

5x102

pH 1

pH 2

pH 3

Am pH 1

Am pH 2

Am pH 3

[Alanine] = 05 M

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

DM

1r Aring

DM

15 M Alanine

10 M Alanine

05 M Alanine

Am 15 M Alanine

Am 10 M Alanine

Am 05 M Alanine

[DTPA] = 0050 M

[HDEHP] = 02 M

Organic Diluent

Dodecane

pH 2

1r Aring


system

111










Lactic

Acid

10 3 0009 380 140 mdash 91







ions including Ln3+

and An3+

Aziz et al67


and Am3+

at pH 36












ion with



112


















113








H7DTPA2+


3+ and Ln






Ln3+

ions is H3DTPA2-

At pH 3 a much







INL

114







115





over Am3+













phase

y = -09383x - 15277 Rsup2 = 09854

y = -11258x + 01381 Rsup2 = 09289

-10

-05

00

05

10

15

20

-125 -12 -115 -11 -105 -1 -095

log

DEu

Am

log [Na5DTPA]

Am Extraction

Eu Extraction

116

Figure 37 Eu3+

Am3+


M) at pH 2










less Am3+







y = -08451x - 14757 Rsup2 = 09936

y = -07958x + 03998 Rsup2 = 0998

-15

-10

-05

00

05

10

15

-11 -1 -09 -08 -07 -06 -05 -04 -03

log

DEu

Am

log [Na5DTPA]


117

Figure 38 Eu3+

Am3+



Figure 39 Eu3+

Am3+



y = 13522x + 02972 Rsup2 = 09283

y = 09682x + 19794 Rsup2 = 09561

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

y = 14702x + 00193 Rsup2 = 09981

y = 11892x + 17129 Rsup2 = 09713

-10

-05

00

05

10

15

20

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

118

Figure 310 Eu3+

Am3+













[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10




y = 11522x - 00047 Rsup2 = 09867

y = 12575x + 18424 Rsup2 = 09976

-10

-05

00

05

10

15

20

25

-05 -04 -03 -02 -01 0 01

log

DEu

Am

log [HDEHP]

Am Extraction

Eu Extraction

119


[HDEHP] (M)

[Na5DTPA]

(M)

02 04 06 08 10

02 012 053 121 126 203

03 010 027 050 077 102

04 008 036 051 077 102



















in Table 35

120













Buffer pH DAm

DEu

SF

Lactic Acid 3 0009 0819 91


2 018 1016 57


2 053 4463 84

3 007 660 99

121


-Ho3+

and Am3+


pH 2 and pH 3






higher pH




Ln3+

Am3+











001

01

1

10

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

His pH 2

His pH 3

Am pH 2

Am pH 3

122












other amino acids

123


2014 32 378-390















2010 28 3 287-312

124


SYSTEM






in an aqueous

phase allowing Ln3+







industrial process









42)

125


(bottom)


vitamin B9 (bottom)






126














Ln3+

separation












to 751

for Ho3+









127



and Eu3+



















and Am3+

Over a



temperature







128

Figure 44 Eu3+

Am3+



tests

Figure 45 Eu3+

Am3+



tests




over Am3+


-02

0

02

04

06

08

1

12

14

16

18

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

-1

-08

-06

-04

-02

0

02

04

06

08

1

12

14

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

129










Figure 46 Eu3+

Am3+









-15

-10

-05

00

05

10

-11 -09 -07 -05 -03

log

DEu

Am

log [GSH]

Am Extraction

Eu Extraction

130

Table 41 Eu3+

Am3+


Na5DTPA at pH 4













131














4 (right)10

132











Figure 410 Eu3+

and Am3+



and Eu3+

Results


y = 19018x2 - 23123x + 72258 Rsup2 = 09937

y = 0442x2 - 03543x + 00659 Rsup2 = 0781

00

00

01

01

02

-20

-10

00

10

20

30

40

50

60

70

-01 26E-15 01 02 03 04 05 06 D

Am

DEu

[Na5DTPA] (M)

Eu extraction

Am extraction

133

Table 42 Eu3+

Am3+































134

Figure 411 Eu3+

and Am3+






Table 43 Eu3+

Am3+















y = -30649x2 + 3243x + 15029 Rsup2 = 09467

y = 00013x + 00015 Rsup2 = 08028

0000

0002

0004

0006

0008

0010

0012

0014

00

05

10

15

20

25

30

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

135

Figure 412 Eu3+

and Am3+



and Eu3+


Table 44 Eu3+

Am3+

















these conditions

y = -01882x + 08847 Rsup2 = 08326

y = 17968x - 04007 Rsup2 = 09946

-0500

0000

0500

1000

1500

2000

00

01

02

03

04

05

06

07

08

09

10

0 02 04 06 08 1 12

DA

m

DEu

[HDEHP] (M)

Eu extraction

Am extraction

136



















0

1

2

3

4

5

6

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Eu3+ in H2O

Eu with GSH

Eu with DTPA

137

























in each case (q)

00

01

02

03

04

05

06

07

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

138


















00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

139


with GSH at pHD 4


[GSH]

(M)


01 1487 428 17

02 785 353 16

03 829 440 11

04 1545 161 58

05 1016 168 52







extraction at



Eu3+






00

01

01

02

02

03

03

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


140


ion is extracted as


spectrum11












00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

141










00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

142



J=1J=2

[GSH] (M)

01 02 03 04 05 st dev t-test

pD 2 0335 0399 0379 0375 0361 0024 No sig diff

pD 3 0440 0433 0451 0439 0419 0012 No sig diff

pD 4 0438 0467 0413 0469 0454 0023 No sig diff

st dev 0060 0034 0036 0048 0047

















143




pH 2 01 1699 plusmn 7 607 plusmn 9 10

pH 2 02 1692 plusmn 10 619 plusmn 10 09

pH 2 03 1686 plusmn 9 629 plusmn 9 09

pH 2 04 1636 plusmn 12 607 plusmn 13 09

pH 2 05 1596 plusmn 11 629 plusmn 13 09

pH 3 01 1755 plusmn 14 626 plusmn 7 09

pH 3 02 1737 plusmn 13 626 plusmn 15 09

pH 3 03 1723 plusmn 5 626 plusmn 13 09

pH 3 04 1720 plusmn 14 635 plusmn 17 09

pH 3 05 1677 plusmn 9 641 plusmn 14 09

pH 4 01 1778 plusmn 14 593 plusmn 16 10

pH 4 02 1747 plusmn 13 640 plusmn 15 09

pH 4 03 1679 plusmn 15 669 plusmn 18 08

pH 4 04 1689 plusmn 14 623 plusmn 15 09

pH 4 05 1679 plusmn 13 652 plusmn 19 08



complex The




GSH with the Eu3+







144















00

05

10

15

20

25

30

35

40

45

50

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Aq

03 M GSH pH 4 Aq

05 M GSH pH 4 Aq

05 M GSH pH 3 Aq

05 M GSH pH 2 Aq

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M GSH pH 4 Org

03 M GSH pH 4 Org

05 M GSH pH 4 Org

05 M GSH pH 3 Org

05 M GSH pH 2 Org

145





as the HDEHPDEHP



ions GSH is




varied

J=1J=2

[GSH] (M)


pD 4 0202 0276 0247 0037 No sig diff

pD 3 - - 0100 - -

pD 2 - - 0500 - -

st dev - - 0202

t-test - - Sig diff







146










0

5

10

15

20

25

30

35

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

0

2

4

6

8

10

12

14

16

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

147



J=1J=2

[Na5DTPA] (M)

005 01 02 03 04 05 06 stdev t-test

D2O 0437 0441 0431 0437 0428 0425 0403 0013

No sig

diff

H2O 0450 0440 0437 0449 0422 0424 0428 0011

No sig

diff


















with GSH

148



[Na5DTPA]

(M)


005 1679 plusmn 3 652 plusmn 2 08

01 1549 plusmn 4 659 plusmn 2 10

02 1348 plusmn 4 666 plusmn 3 09

03 1179 plusmn 4 665 plusmn 3 08

04 1076 plusmn 4 674 plusmn 4 07

05 978 plusmn 4 698 plusmn 4 05

06 916 plusmn 5 714 plusmn 5 03






extraction with



0

1

2

3

4

5

6

7

550 600 650 700

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

149








phase





J=1J=2 0552 0578 0502 0039 No sig

diff






and 426

150














J=1J=2 0472 0499 0455 0510 0025 No sig

diff

00

02

04

06

08

10

12

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Aq

06 M HDEHP Aq

08 M HDEHP Aq

10 M HDEHP Aq

151





The lowest Eu3+



concentrations Am3+








Facility using a 60



seen in Figure 427

00

00

00

01

01

01

01

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

04 M HDEHP Org

06 M HDEHP Org

08 M HDEHP Org

10 M HDEHP Org

152











00

01

01

02

02

03

03

04

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

005 M DTPA

01 M DTPA

02 M DTPA

03 M DTPA

04 M DTPA

05 M DTPA

06 M DTPA

153




[Na5DTPA] (M)

01 02 03 04 05 06 st

dev

t-test

J=1J=2 0477 0481 0452 0401 0407 0411 0036

No sig

diff



kGy γ-radiation


01 648 plusmn 4 1895 plusmn 12 10

02 661 plusmn 6 1678 plusmn 10 09

03 670 plusmn 6 1536 plusmn 11 08

04 679 plusmn 5 1462 plusmn 9 07

05 701 plusmn 7 1328 plusmn 10 05

06 696 plusmn 6 1211 plusmn 8 03






154


extraction from


range of 01-06 M















J=1J=2 0505 0563 0551 0031 No sig diff



under a variety



0

1

2

3

4

5

6

7

8

9

10

550 600 650 700

Emis

sio

n In

ten

sity

(au

) Hu

nd

red

s

Wavelength (nm)

01 M DTPA Aq

03 M DTPA Aq

05 M DTPA Aq

01 M DTPA Org

03 M DTPA Org

05 M DTPA Org

155



Also like Eu3+



441 Dy3+







is relatively








6H152 and

7F92 rarr







00

02

04

06

08

10

12

14

16

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O

Dy DTPA

Dy GSH

7F92 rarr

6H152

7F92 rarr

6H132

156







352 nm









lanthanides







00

02

04

06

08

10

12

14

425 475 525 575 625 675

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Dy H2O Aq

Dy DTPA Aq

Dy GSH Aq

Dy H2O Org

Dy DTPA Org

Dy GSH Org

157



excitation







Systems at pH 4

The Dy3+



Eu3+

Tb3+

and Dy3+




irradiation





data

00

01

02

03

04

05

06

07

08

09

10

550 560 570 580 590

Emis

sio

n In

ten

sity

(au

) x 1

00

00

Wavelength (nm)

pH 2 Aq

pH 3 Aq

pH 4 Aq

pH 4 (03 M DTPA) Aq

pH 2 Org

pH 3 Org

pH 4 Org


158


10 mM Dy3+

) in H2O


397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


10 mM Dy3+

) with


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

0

5

10

15

20

25

30

35

40

45

50

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) H

un

dre

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

0

2

4

6

8

10

12

14

16

18

20

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Sm

Eu

Tb

Dy

159


10 mM Dy3+

005 M


397 nm for

Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)








complex can also be

seen for the Tb3+



or Dy3+




Ln3+


Ln3+

with

GSH



0

1

2

3

4

5

6

7

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

160





and Tb3+

as calculations of

q for Sm3+

and Dy3+




ion with




and Tb3+

samples at pH 4


Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)

Ln3+


Ln3+

with

GSH











and Tb3+

are as



161


10 mM Dy3+

) with


397

nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


pH range of 2-4







and Tb3+

samples before



Eu (III)

H2O

Eu (III)

D2O

Tb(III)

H2O

Tb (III)

D2O

Eu(III) Tb(III)




00

10

20

30

40

50

60

70

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm

Eu

Tb

Dy

162





with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

00

05

10

15

20

25

30

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

163


with 05 M GSH



397 nm for Eu3+

366 nm for Tb3+

and 352 nm for Dy3+

)







and Dy3+



and Eu3+





the Ln3+



Ln3+


MS






00

05

10

15

20

25

30

35

450 500 550 600 650 700 750

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Sm Aq

Eu Aq

Tb Aq

Dy Aq

Sm Org

Eu Org

Tb Org

Dy Org

164







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

0

5

10

15

20

25

30

35

56 57 58 59 60 61 62 63 64 65 66 67 68

Dis

trib

uti

on

Rat

io

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

Am3+

165

















166



pH

[GSH]

(M)

SF


2 01 234 171 148 107 136 158 216 222 237 234

2 02 244 176 145 103 134 146 215 229 239 244

2 03 263 183 145 105 137 165 243 244 281 289

2 04 239 170 151 111 145 168 218 237 259 265

2 05 278 197 164 117 162 189 257 269 300 314

3 01 1735 972 477 276 163 104 112 53 41 38

3 02 1953 841 433 256 320 266 290 130 89 77

3 03 1898 785 388 220 152 90 95 39 28 24

3 04 2046 812 412 243 196 121 126 53 38 34

3 05 2145 705 312 139 36 16 20 04 02 00

4 01 3777 141 12 - - - - - - -

4 02 5548 231 36 06 - - - - - -

4 03 2768 239 27 - - - - - - -

4 04 1620 150 21 01 - - - - - -

4 05 1589 286 48 11 - - - - - -







167

GSH0011resp

45 40 35 30 25 20 15 10


0

005

010

Norm

alized Inte

nsity

197201200100200099

c

d

gb

i

f

44

944

844

6

38

9

37

637

437

2

28

628

628

528

4

24

924

824

724

624

524

4

21

120

920

720

5


45 40 35 30 25 20 15 10


0

005

010

015

020

025

Norm

alized Inte

nsity

133151244272014101206498131111059100

m

c

d

n

g

q

b

l

i

p

f

47

0

44

7 44

544

442

942

841

641

541

140

940

940

738

137

737

537

3

36

736

6

29

929

728

428

328

1

26

7

24

6

24

424

324

223

823

022

822

6

20

720

520

419

6

19

519

419

319

1

a

b

168

Eu GSH0011resp

45 40 35 30 25 20 15 10


005

010

015

Norm

alized Inte

nsity

035183050206177050088216024026100

d

g

b

i

f

c

45

044

844

7

42

0 41

841

741

341

241

138

0 37

837

737

136

9 30

230

1

28

928

728

628

428

328

1

25

124

924

724

624

424

2 23

3 23

122

921

020

820

720

519

919

819

719

6

GSH DTPA0011resp

45 40 35 30 25 20 15 10


0

005

010

015

Norm

alized Inte

nsity

032158045179156092075366021025099

c

d

g

DTPA

DTPA

DTPA

b

DTPA

i

f

45

044

9 44

744

6

41

941

841

741

241

141

0

37

937

737

537

036

8

34

133

633

5

30

730

530

1

28

928

628

528

428

228

0

25

024

824

624

524

324

1 23

223

022

821

020

820

620

419

719

5

c

d

169

EuDTPA GSH0011resp

45 40 35 30 25 20 15 10


0

0005

0010

0015

0020

0025

0030

0035

0040

0045

0050

0055

Norm

alized Inte

nsity

180181200200212103673021100

47

0

44

244

1

38

4

36

836

3

32

832

0 30

230

129

9 28

628

528

328

1

24

724

624

524

424

3

20

820

720

520

3




Figure 442 1H





e

170













422)









and Am3+

when used without

Na5DTPA





Eu3+

and Am3+





experiments






171


extraction























with pH







conditions






172





irradiation











Dy3+




decreasing as


for Tb3+

and Dy3+


and Eu3+













173

















Chem B 2012 116 46 13722-13730


Chem 2010 8 4915-4920



174











) ions


by HDEHP (di-



considered






the MA3+



over Ln3+

This is













INE

175





















Protected

Protected Protected

176













0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

177






Eu3+




centre as expected


complexes at pD 2-4

0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

0

5

10

15

20

25

30

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

178

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pD 2 0359 0381 0404 0353 0023

No sig

diff

pD 3 0394 0425 0417 0381 0020

No sig

diff

pD 4 0391 0427 0432 0423 0019

No sig

diff

st dev 0019 0026 0014 0035

t-test No sig

diff

No sig

diff

No sig

diff

No sig

diff












179



excitation

















itself








180




at 397 nm


extraction from



0

0

0

0

0

1

1

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

0

10

20

30

40

50

60

70

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


181


extraction from




extraction from



0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)


0

1

2

3

4

5

6

7

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA Aq

Arg-DTPA Aq

His-DTPA Aq

Ser-DTPA Aq

Ala-DTPA Org

Arg-DTPA Org

His-DTPA Org

Ser-DTPA Org

182























Eu3+


pH 2-4

DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

pH 2 0208 0207 0198 0208 0005 No sig diff

pH 3 0210 0213 0311 0347 0069 Sig diff

pH 4 0182 0210 0206 0205 0013 No sig diff

st dev 0016 0003 0063 0081


183












397 nm





0

5

10

15

20

25

30

35

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)

Ala-DTPA

Arg-DTPA

His-DTPA

Ser-DTPA

184



DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-


J=1J=2 0357 0395 0412 0362 0026 No sig

diff













extraction from



0

1

2

3

4

5

6

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) Th

ou

san

ds

Wavelength (nm)


185












DTPA-

(AlaOMe)2

DTPA-

(ArgOMe)2

DTPA-

(HisOMe)2

DTPA-

(SerOEt)2

st dev t-test

J=1J=2 0241 0233 0198 0231 0019

No sig

diff





without irradiation

(micros)


irradiation









186



Am + 152

Eu (1 kBq mL-1






and Eu3+








and Eu3+

for these











Am3+

using DTPA-


187


Am3+

using DTPA-



Am3+

using DTPA-




Am3+





and Am3+

can be seen in


Am3+

(as

188

Nd3+









189







190






complex to Eu3+





over Am3+





with the ligands








between Ln3+

Am3+






Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30








191






192





and MA3+




allowing Ln3+












from Ln3+

23









Ln3+




Am3+

is achieved








organic phase

193


keeping Am3+

















lanthanides



and [Eu(DTPA)]2-






Eu3+




ion when



and Cm3+





or Cm3+




194







and the



operation








and Am3+

when used without

Na5DTPA






Eu3+

and Am3+




the pH is increased







Am3+


TALSPEAK process



195

































can occur Further




Eu3+

Tb3+

and Dy3+






196




and Dy3+

which are


and Eu3+



-Ho3+






acid systems



Eu3+

Am3+









MA3+







at pH 2 3 and 4











irradiation



between Ln3+

Am3+


197





Ce3+

and Pr3+



and for the Dy3+

Nd3+


DyNd ~ 30



















the use of amino







with lactate15


Cm3+

with DTPA16


with





however there are



198

62 Future Work
















199




















and Cm3+














ratio of Am3+





200




10 245-279



523-526






2014 32 378-390





47 8856



2012 65 16 2862-2876











amino-acidshtm 2015




201
























were returned


amp An3+









202






Stock solutions




0625 M L-Phe in D2O







1 M amino








Equation 71









203







such as from a 60




H2O rarr H + OH

OH + Fe2+

rarr Fe3+

+ HO-

H + O2 rarr HO2

H+ + Fe

2+ + HO2 rarr Fe

3+ + H2O2

H2O2 + Fe2+

rarr Fe(OH)2+

+ OH

HO2 + Fe3+

rarr Fe2+

+ O2 + H+


ions to Fe3+

The amount

of Fe3+





out using the 60










72)2

204

Equation 72

Where


-1


cm-1









For γ-rays

εFe(III) = 2197 M-1

cm-1


Equation 73

Equation 74





205




min-1

)

1 1084678

2 1171864

3 1183066

4 1103841


INL









Stock solutions

1 M Na5DTPA in H2O

1 M L-Ala in H2O














206




















Stock solutions

1 M Na5DTPA in H2O











207






















732 Gamma counting










microL 241

Am or 154



208






Am or 154


) were also



733 ICP-MS




of each of La
























209

Stock solutions
























performed at INL







210


















(145 g 6 mmol)

Yields


)


)


)


)





[M+Na]+ and [M+K]






found in Appendix 6

211


+ 603 (39) [M+K]

+


+ 772 (9) [M+K]

+


+ 662 (15) [M+K]

+


+ 735 (10) [M+K]

+







spectra 13




1H









3JHH =100 Hz 4 H


4 H H2) 375 - 387 (m 4 H H3) 418 - 425 (m 2 H H1)


3JHH 730 Hz 4 H H9) 169 - 189


365 (s 6 H H7) 368 (s 2 H H6) 375 - 384 (m 4 H H3) 436 - 444 (m 2 H H1)



Hz 4 H H8) 452 (dd 3JHH =479 378 Hz 2 H H1)


(s 4 H H3) 358 (s 6 H H7) 362 (m 2 H H6) 370 - 375 (m 1 H H3) 464 - 466

(m 2 H H1) 714 (s 2 H H9) 843 (s 2 H H10)

212




213


7532 13

C NMR Spectroscopy




1718 (q-C C11) 1721 (q-C C10) 1746 (q-C C8)




C10) 1735 (q-C C8)



1693 (q-C C9) 1712 (q-C C10) 1717 (q-c C11) 1723 (CH3 C8)



1286 (q-C C13) 1333 (CH C15) 1711 (q-C C9) 1714 (q-C C11) 1716 (q-C

C10) 1746 (q-C C8)

214

Figure 75 13


Figure 76 13


Figure 77 13


215

Figure 78 13










C () H () N () Cl () Na ()


DTPA-(AlaOMe)2

4689 4224 662 685 1243 1146 0 475 0 0

DTPA-(ArgOMe)2

4583 3896 701 637 2100 1643 0 1427 0 0

DTPA-(SerOEt)2

4622 4300 663 755 1123 1041 0 240 0 0

DTPA-(HisOMe)2

4834 3985 594 668 1812 1458 0 595 0 0

216






Stock solutions



















using the 60






217

76 Instruments


Co Irradiator


Co



Co to 60







Figure 79 60













218


ions






20 minutes




400





Ln3+


Eu 617 395

Tb 545 379

Sm 600 403

Dy 575 352

219






220

APPENDICES








00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

221




00

02

04

06

08

10

12

14

550 600 650 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

222







0

5

10

15

20

25

30

35

40

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

0

50

100

150

200

250

56 57 58 59 60 61 62 63 64 65 66 67 68

Sep

arat

ion

Fac

tor

Atomic Number

01 M GSH

02 M GSH

03 M GSH

04 M GSH

05 M GSH

223


(1 mM)


mM)


DTPA-(AlaOMe)2 243

DTPA-(ArgOMe)2 238

DTPA-(SerOEt)2 240

DTPA-(HisOMe)2 286

224




0

2

4

6

8

10

12

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

0

2

4

6

8

10

12

14

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

225


0

1

2

3

4

5

6

7

8

9

10

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

226







00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

tem

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

227



00

05

10

15

20

25

550 575 600 625 650 675 700

Emis

sio

n In

ten

sity

(au

) x

10

00

0

Wavelength (nm)

Ala-DTPA

Arg-DTPA

Hist-DTPA

Ser-DTPA

228


[M+H]+

[M+Na]+ [M+K]

+

229

AP

PE

ND

IX 7

- 1H N

MR

spectru

m fo

r DT

PA

-(AlaO

Me)

2

230

GSH1ESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alize

d In

tensi

ty

Water

44

944

844

6

38

9

37

6 37

437

2 28

628

628

528

4

24

924

8 24

724

624

524

4

21

1 20

920

720

5

AP

PE

ND

IX 8

- 1H N

MR

spectru

m fo

r GS

H

231

EUGSHESP

45 40 35 30 25 20 15


01

02

03

04

05

06

07

08

09

Norm

alized Inte

nsity

Water

45

044

844

7

41

8

38

037

837

7

37

136

9

30

230

1

28

7 28

628

4

24

9 24

724

624

423

323

1

21

020

820

720

5

AP

PE

ND

IX 8

a - 1H N

MR

spectru

m fo

r Eu(N

O3 )

3 + G

SH

232

development of a simplified soft-donor technique for

Documents