Contents. Preface V List of Contributing Authors. Alfred Golloch 1 Introduction 1 References 3

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1 Contents Preface V List of Contributing Authors XV Alfred Golloch 1 Introduction 1 References 3 Alfred Golloch 2 Analytics of Rare Earth Elements - Basics and Methods Electronic configurations of RE elements and analytical properties Chemistry of Ln3+ ions Chemistry of Ln2+ and Ln4+ ions The development of rare earth analytics from 1940 to present Determination methods applied during the period from 1940 to Separation methods applied during the period RE analysis during the period Literature review Situation of RE analytics from 1980 to present 12 References 12 Bin Hu, Man He, Beibei Chen and Zucheng Jiang 3 Separation/Preconcentration Techniques for Rare Earth Elements Analysis 3.1 Introduction Chemical separation techniques for REEs Precipitation/coprecipitation Liquid-liquid extraction Affecting factors for LLE of REEs Extractants for REEs Extractant concentration and extraction equilibrium constant Medium ph Salting-out agent Extraction systems for REEs and their application Liquid phase microextraction Operation modes and mechanism Single-drop microextraction Hollow fiber liquid phase microextraction 37

2 3.4.4 Two-phase HF-LPME Three-phase HF-LPME Dispersive liquid-liquid microextraction Solidified floating organic drop microextraction Affecting factors in LPME Cloud point extraction Solid phase extraction Carbon nanotubes and graphene oxide Silica-based materials Chelating resin and ionic-exchange resin Metal oxide nanostructured materials Ion-imprinted materials Metal-organic frameworks (MOFs) Restricted access materials Capillary microextraction 61 References 65 Beibei Chen, Man He, Huashan Zhang, Zucheng Jiang and Bin Hu 4 Chromatographic Techniques for Rare Earth Elements Analysis 4.1 Introduction Liquid chromatography Ion-exchange chromatography Ion chromatography Reverse-phase ion pair chromatography (RPIPC) Extraction chromatography Thin layer chromatography (TLC) and Paper chromatography (PC) Gas chromatography Capillary Electrophoresis (CE) Basic knowledge and principle Influencing factors on CE separation Applications in REEs analysis Supercritical fluid chromatography 115 References 116 Lena Teigmann, Uwe Lindner, Jana Lingott and Norbert Jakubowski 5 Analysis and Speciation of Lanthanoides by ICP-MS Introduction Fundamentals of ICP-MS Sample preparation Sample introduction The ion source

3 5.2.4 Interface Lens system Mass analyzers Detector and computer Analytical figures of merit Speciation of Gd-based contrast agents Analysis of Gd-based contrast agents in medical samples Analysis of Gd-based contrast agents in environmental samples Summary and outlook 142 References 142 Man He, Bin Hu, Beibei Chen and Zucheng Jiang 6 Inductively Coupled Plasma Optical Emission Spectrometry for Rare Earth Elements Analysis Introduction Spectral interference Matrix effect Acid effect Sensitivity-enhancing effect of organic solvent Sample introduction for ICP Pneumatic nebulization and ultrasonic nebulization Flow injection Laser ablation Electrothermal vaporization ETV-ICP-OES for REE analysis Fluorination-assisted (F)ETV-ICP-OES for REEs analysis Low-temperature ETV-ICP-OES for REEs analysis Application of ICP-OES in the analysis of high-purity REE, alloys and ores High-purity REE analysis by ICP-OES REE ores analysis by ICP-OES Trace REE analysis by ICP-OES in alloys References 193 JörgNiederstraßer 7 Application of Spark Atomic Emission Spectrometry for the Determination of Rare Earth Elements in Metals and Alloys Introduction Spark emission spectrometry basics Setup of a spark emission spectrometer 200

4 7.3.1 Argon supply Spark stand Spectrometer optical system Spark generator Power supply Operation and evaluation PC The analysis process Quantitative analysis Calibration and recalibration Evaluation of calibration and analysis results Using spark emission spectrometry Analysing rare earths using spark emission spectrometry Industrial use of rare earths Spectrometric prerequisites Calibration samples Analysis of aluminium alloys Calibration (analysis function) and accuracy Detection lim its Repeatability Analysis of magnesium alloys Calibration (analysis function) and accuracy Detection limits Repeatability Analysis of iron alloys Calibration (analysis function) and accuracy Detection lim its Repeatability Long-term stability Analysis of zinc alloys Calibration (analysis function) and accuracy Detection limits Repeatability Conclusion References 229 Rainer Schramm 8 Use of X-ray Fluorescence Analysis for the Determination of Rare Earth Elements Introduction Principle of X-ray fluorescence analysis XRF methods Energy-dispersive X-ray fluorescence analysis 233

5 8.3.2 Wavelength-dispersive X-ray analysis Comparison of EDXRF-WDXRF Other XRF techniques Sample preparation Pressed pellets techniques Fusion technology Additional sample preparation techniques Practical application of REEs determination Reference materials Measuring parameters Analyte lines Lower limit of detection (LLD) Calibration Other calibration strategies mentioned in literature Summary References 251 Heinz-Günter Stosch 9 Neutron Activation Analysis of the Rare Earth Elements (REE) - With Emphasis on Geological Materials Introduction Principles of neutron activation: activation equation, cross sections Equipment Neutron sources The counting system Practical considerations Instrumental versus radiochemical NAA Samples and standards Counting strategies Radiochemical neutron activation analysis (RNAA) - a fast separation scheme Data reduction and sources of error Conclusion Acknowledgements 283 References 284 Sven Sindern and F. Michael Meyer 10 Automated Quantitative Rare Earth Elements Mineralogy by Scanning Electron Microscopy Introduction Quantitative mineralogy Scanning electron microscopy 289

6 10.4 SEM-based automated quantitative mineralogy Quantitative Evaluation of Minerals by Scanning Electron Microscopy Mineral Liberation Analyser Tescan-Integrated Mineral Analyser ZEISS Mineralogie Mining Quantitative REE mineralogy Concluding remarks 298 Acknowledgements 298 References 299 Larissa Müller, Heike Traub and Norbert Jakubowski 11 Novel Applications of Lanthanoides as Analytical or Diagnostic Tools in the Life Sciences by ICP-MS-based Techniques Introduction Bio-conjugation of biomolecules Fundamentals Bio-conjugation of antibodies Applications Development of identification and quantification strategies for DNA, peptides and proteins in mass spectrometry Analytical and diagnostic applications of lanthanoides Outlook 316 References 317 Jürgen Meinhardt, Martin Kilo, Ferdinand Somorowsky and Werner Hopp 12 Lanthanoides in Glass and Glass Ceramics Introduction Literature survey of rare earth chemical analysis in glass Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) Laser-ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES) ICP-MS analysis of solutions X-ray fluorescence analysis (XRF) Analytical methods for the determination of main components of glass (except lanthanoides) Preparation of sample solutions for glass analysis by ICP-OES Hydrofluoric acid digestion Melt digestion

7 12.5 ICP-OES analysis of rare earth elements Analysis of special optical glass Analysis of glass by topochemical analysis 327 References 331 Sven Sindern 13 Analysis of Rare Earth Elements in Rock and Mineral Samples by ICP-MS and LA-ICP-MS Introduction Technical development Physical and chemical effects on concentration and isotope ratio determination Determination of REE concentrations Sample preparation Quantification Determination of isotope ratios by multi-collector (MC)-ICP-MS Solution-MC-ICP-MS LA-MC-ICP-MS Concluding remarks 349 Acknowledgements 349 References 349 Tom Lorenz and Martin Bertau 14 Recycling of Rare Earth Elements Recycling of rare earth elements Recycling from fluorescent lamp scraps Starting material Solid-state chlorination Optimization of the solid-state chlorination Recycling process Summary RE metal recycling from Fe14Nd2B magnets Starting material Preliminary tests Optimization of the solid-state chlorination Recycling process Summary References 391 Index 395