Preface

Contents

List of Contributing Authors

1. Introduction

References

2. Analytics of Rare Earth Elements – Basics and Methods

2.1 Electronic configurations of RE elements and analytical properties

2.1.1 Chemistry of Ln3+ ions

2.1.2 Chemistry of Ln2+ and Ln4+ ions

2.2 The development of rare earth analytics from 1940 to present

2.2.1 Determination methods applied during the period from 1940 to 1960

2.2.2 Separation methods applied during the period 1940–1960

2.2.3 RE analysis during the period 1960–1980

2.2.4 Literature review 1978

2.2.5 Situation of RE analytics from 1980 to present

References

3. Separation/Preconcentration Techniques for Rare Earth Elements Analysis

3.1 Introduction

3.2 Chemical separation techniques for REEs

3.2.1 Precipitation/coprecipitation

3.3 Liquid–liquid extraction

3.3.1 Affecting factors for LLE of REEs

3.3.2 Extractants for REEs

3.3.3 Extractant concentration and extraction equilibrium constant

3.3.4 Medium pH

3.3.5 Salting-out agent

3.3.6 Extraction systems for REEs and their application

3.4 Liquid phase microextraction

3.4.1 Operation modes and mechanism

3.4.2 Single-drop microextraction

3.4.3 Hollow fiber liquid phase microextraction

3.4.4 Two-phase HF-LPME

3.4.5 Three-phase HF-LPME

3.4.6 Dispersive liquid–liquid microextraction

3.4.7 Solidified floating organic drop microextraction

3.4.8 Affecting factors in LPME

3.4.9 Cloud point extraction

3.5 Solid phase extraction

3.5.1 Carbon nanotubes and graphene oxide

3.5.2 Silica-based materials

3.5.3 Chelating resin and ionic-exchange resin

3.5.4 Metal oxide nanostructured materials

3.5.5 Ion-imprinted materials

3.5.6 Metal-organic frameworks (MOFs)

3.5.7 Restricted access materials

3.5.8 Capillary microextraction

References

4. Chromatographic Techniques for Rare Earth Elements Analysis

4.1 Introduction

4.2 Liquid chromatography

4.2.1 Ion-exchange chromatography

4.2.2 Ion chromatography

4.2.3 Reverse-phase ion pair chromatography (RPIPC)

4.2.4 Extraction chromatography

4.2.5 Thin layer chromatography (TLC) and Paper chromatography (PC)

4.3 Gas chromatography

4.4 Capillary Electrophoresis (CE)

4.4.1 Basic knowledge and principle

4.4.2 Influencing factors on CE separation

4.4.3 Applications in REEs analysis

4.5 Supercritical fluid chromatography

References

5. Analysis and Speciation of Lanthanoides by ICP-MS

5.1 Introduction

5.2 Fundamentals of ICP-MS

5.2.1 Sample preparation

5.2.2 Sample introduction

5.2.3 The ion source

5.2.4 Interface

5.2.5 Lens system

5.2.6 Mass analyzers

5.2.7 Detector and computer

5.3 Analytical figures of merit

5.4 Speciation of Gd-based contrast agents

5.5 Analysis of Gd-based contrast agents in medical samples

5.6 Analysis of Gd-based contrast agents in environmental samples

5.7 Summary and outlook

References

6. Inductively Coupled Plasma Optical Emission Spectrometry for Rare Earth Elements Analysis

6.1 Introduction

6.1.1 Spectral interference

6.1.2 Matrix effect

6.1.3 Acid effect

6.1.4 Sensitivity-enhancing effect of organic solvent

6.2 Sample introduction for ICP

6.2.1 Pneumatic nebulization and ultrasonic nebulization

6.2.2 Flow injection

6.2.3 Laser ablation

6.2.4 Electrothermal vaporization

6.3 ETV-ICP-OES for REE analysis

6.3.1 Fluorination-assisted (F)ETV-ICP-OES for REEs analysis

6.3.2 Low-temperature ETV-ICP-OES for REEs analysis

6.4 Application of ICP-OES in the analysis of high-purity REE, alloys and ores

6.4.1 High-purity REE analysis by ICP-OES

6.4.2 REE ores analysis by ICP-OES

6.4.3 Trace REE analysis by ICP-OES in alloys

References

7. Application of Spark Atomic Emission Spectrometry for the Determination of Rare Earth Elements inMetals and Alloys

7.1 Introduction

7.2 Spark emission spectrometry basics

7.3 Setup of a spark emission spectrometer

7.3.1 Argon supply

7.3.2 Spark stand

7.3.3 Spectrometer optical system

7.3.4 Spark generator

7.3.5 Power supply

7.3.6 Operation and evaluation PC

7.4 The analysis process

7.5 Quantitative analysis

7.5.1 Calibration and recalibration

7.5.2 Evaluation of calibration and analysis results

7.6 Using spark emission spectrometry

7.7 Analysing rare earths using spark emission spectrometry

7.7.1 Industrial use of rare earths

7.7.2 Spectrometric prerequisites

7.7.3 Calibration samples

7.8 Analysis of aluminium alloys

7.8.1 Calibration (analysis function) and accuracy

7.8.2 Detection limits

7.8.3 Repeatability

7.9 Analysis of magnesium alloys

7.9.1 Calibration (analysis function) and accuracy

7.9.2 Detection limits

7.9.3 Repeatability

7.10 Analysis of iron alloys

7.10.1 Calibration (analysis function) and accuracy

7.10.2 Detection limits

7.10.3 Repeatability

7.10.4 Long-term stability

7.11 Analysis of zinc alloys

7.11.1 Calibration (analysis function) and accuracy

7.11.2 Detection limits

7.11.3 Repeatability

7.12 Conclusion

References

8. Use of X-ray Fluorescence Analysis for the Determination of Rare Earth Elements

8.1 Introduction

8.2 Principle of X-ray fluorescence analysis

8.3 XRF methods

8.3.1 Energy-dispersive X-ray fluorescence analysis

8.3.2 Wavelength-dispersive X-ray analysis

8.3.3 Comparison of EDXRF–WDXRF

8.3.4 Other XRF techniques

8.4 Sample preparation

8.4.1 Pressed pellets techniques

8.4.2 Fusion technology

8.4.3 Additional sample preparation techniques

8.5 Practical application of REEs determination

8.5.1 Reference materials

8.5.2 Measuring parameters

8.5.3 Analyte lines

8.5.4 Lower limit of detection (LLD)

8.6 Calibration

8.6.1 Other calibration strategies mentioned in literature

8.7 Summary

References

9. Neutron Activation Analysis of the Rare Earth Elements (REE) – With Emphasis on Geological Materials

9.1 Introduction

9.2 Principles of neutron activation: activation equation, cross sections

9.3 Equipment

9.3.1 Neutron sources

9.3.2 The counting system

9.4 Practical considerations

9.4.1 Instrumental versus radiochemical NAA

9.4.2 Samples and standards

9.4.3 Counting strategies

9.4.4 Radiochemical neutron activation analysis (RNAA) – a fast separation scheme

9.4.5 Data reduction and sources of error

9.5 Conclusion

Acknowledgements

References

10. Automated Quantitative Rare Earth Elements Mineralogy by Scanning Electron Microscopy

10.1 Introduction

10.2 Quantitative mineralogy

10.3 Scanning electron microscopy

10.4 SEM-based automated quantitative mineralogy

10.4.1 Quantitative Evaluation of Minerals by Scanning Electron Microscopy

10.4.2 Mineral Liberation Analyser

10.4.3 Tescan-Integrated Mineral Analyser

10.4.4 ZEISS Mineralogic Mining

10.5 Quantitative REE mineralogy

10.6 Concluding remarks

Acknowledgements

References

11. Novel Applications of Lanthanoides as Analytical or Diagnostic Tools in the Life Sciences by ICP-MS-based Techniques

11.1 Introduction

11.2 Bio-conjugation of biomolecules

11.2.1 Fundamentals

11.2.2 Bio-conjugation of antibodies

11.3 Applications

11.3.1 Development of identification and quantification strategies for DNA, peptides and proteins in mass spectrometry

11.3.2 Analytical and diagnostic applications of lanthanoides

11.4 Outlook

References

12. Lanthanoides in Glass and Glass Ceramics

12.1 Introduction

12.2 Literature survey of rare earth chemical analysis in glass

12.2.1 Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

12.2.2 Laser-ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES)

12.2.3 ICP-MS analysis of solutions

12.2.4 X-ray fluorescence analysis (XRF)

12.3 Analytical methods for the determination of main components of glass (except lanthanoides)

12.4 Preparation of sample solutions for glass analysis by ICP-OES

12.4.1 Hydrofluoric acid digestion

12.4.2 Melt digestion

12.5 ICP-OES analysis of rare earth elements

12.6 Analysis of special optical glass

12.7 Analysis of glass by topochemical analysis

References

13. Analysis of Rare Earth Elements in Rock and Mineral Samples by ICP-MS and LA-ICP-MS

13.1 Introduction

13.2 Technical development

13.3 Physical and chemical effects on concentration and isotope ratio determination

13.4 Determination of REE concentrations

13.4.1 Sample preparation

13.4.2 Quantification

13.5 Determination of isotope ratios by multi-collector (MC)-ICP-MS

13.5.1 Solution-MC-ICP-MS

13.5.2 LA-MC-ICP-MS

13.6 Concluding remarks

Acknowledgements

References

14. Recycling of Rare Earth Elements

14.1 Recycling of rare earth elements

14.2 Recycling from fluorescent lamp scraps

14.2.1 Starting material

14.2.2 Solid-state chlorination

14.2.3 Optimization of the solid-state chlorination

14.2.4 Recycling process

14.2.5 Summary

14.3 RE metal recycling from Fe14Nd2Bmagnets

14.3.1 Starting material

14.3.2 Preliminary tests

14.3.3 Optimization of the solid-state chlorination

14.3.4 Recycling process

14.3.5 Summary

References

Index