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138La-138Ce Systematics in Terrestrial Samples and Chondrites

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138La-138Ce Systematics in Terrestrial Samples and Chondrites 138La-138Ce systematics in terrestrial samples and chondrites Inaugural-Dissertation zur Erlangung des Doktorgrades der Mathematisch-Naturwissenschaftlichen Fakultät der Universität zu Köln vorgelegt von Christiane Schnabel aus Wagna Köln, 2019 Gutachter: Prof. Dr. Carsten Münker PD. Dr. Erik Strub Tag der mündlichen Prüfung: 16.01.2020 Table of content Abstract ................................................................................................................................. 3 Kurzzusammenfassung ......................................................................................................... 5 1. Chapter 1 ....................................................................................................................... 7 Introduction ........................................................................................................................... 7 1.1. Aim of this study and overview of the chapters ........................................................ 7 1.2. The origin of the elements ....................................................................................... 7 1.3. Primordial nucleosynthesis ...................................................................................... 7 1.4. Stellar nucleosynthesis ............................................................................................ 9 1.5. Nucleosynthesis of heavier elements .....................................................................10 1.6. Consequences of nucleosynthesis for Ce ...............................................................11 1.7. Evolution of the solar system ..................................................................................13 1.8. Meteorites ..............................................................................................................13 1.9. Chondrite classes ...................................................................................................14 1.10. The Geochemistry of Lanthanum and Cerium .....................................................16 1.11. The 138La-138Ce Geochronometer ........................................................................17 1.12. Chondritic Earth: CHUR value ............................................................................19 1.13. Non-chondritic Earth ...........................................................................................22 1.14. Earth’s oldest rocks ............................................................................................24 1.15. Crust-Mantle Models ...........................................................................................26 2. Chapter 2 ......................................................................................................................31 La–Ce isotope measurements by multicollector- ICPMS ......................................................31 2.1. Introduction ............................................................................................................31 2.2. Analytical Protocols ................................................................................................33 2.3. Reagents and sample digestion procedures. ..........................................................33 2.4. Chemical separation procedures for Cerium isotope measurements (Ce-IC) and La- Ce concentration measurements (La-Ce-ID). ....................................................................34 2.5. Preparation of a mixed La-Ce isotope tracer ..........................................................37 2.6. La-Ce measurements by MC-ICP-MS ....................................................................39 2.7. Ce-IC Measurements. ............................................................................................39 2.8. La/Ce-isotope dilution (ID) measurements .............................................................43 2.9. Cerium isotope compositions of synthetic reference materials and rock standards.44 2.10. Synthetic Reference Materials (JMC-304, Cologne and Mainz-AMES batches). .44 2.11. Recalculation relative to the chondritic uniform reservoir (CHUR) value. ............48 2.12. Cerium isotope composition and La-Ce concentration measurements for geological reference materials. .........................................................................................48 2.13. Conclusions ........................................................................................................54 3. Chapter 3 ......................................................................................................................56 The Ce isotope composition and La/Ce value of CHUR .......................................................56 1 3.1. Introduction ............................................................................................................56 3.1.1. Previous CHUR estimates for the 138La–138Ce system and data comparison ......57 3.2. Analytical methods and samples ............................................................................62 3.2.1. Meteorite samples analyzed in this study ............................................................62 3.2.2. Sample preparation and ion-exchange chromatography .....................................63 3.2.3. Mass spectrometry .............................................................................................64 3.3. Results ...................................................................................................................65 3.3.1. Selection of data for the CHUR determination ....................................................69 3.4. Discussion ..............................................................................................................71 3.4.1. Cerium isotope data and standard reference materials .......................................71 3.4.2. Lanthanum-Cerium concentration data ...............................................................72 3.4.3. Calculation of the mean 138Ce/136Ce and 138La/136Ce CHUR values .....................76 3.4.4. Implications for terrestrial La-Ce systematics ......................................................80 3.5. Conclusions............................................................................................................83 4. Chapter 4 ......................................................................................................................85 Combined 138La-138Ce, 147Sm-143Nd and 176Lu-176Hf isotope systematics in early Archean rocks from southern West Greenland and South Africa ........................................................85 4.1. Introduction ............................................................................................................85 4.2. Geological Overview ..............................................................................................86 4.3. Analytical methods .................................................................................................90 4.3.1. Sample preparation and ion-exchange chromatography .....................................90 4.3.2. Mass spectrometry .............................................................................................91 4.4. Results ...................................................................................................................92 4.4.1. Present day ε143Nd(0)/ε176Hf(0) and ε138Ce(0) values ..........................................96 4.4.2. ε143Nd(t)/ε176Hf(t) and ε138Ce(t) values .................................................................98 4.5. Discussion ............................................................................................................ 102 4.5.1. Influence of alteration and metamorphism on the La-Ce isotope composition ... 102 4.5.2. Cerium anomalies ............................................................................................. 105 4.5.3. Effects of Sediment recycling on source compositions ...................................... 107 4.5.4. 138La-138Ce CHUR value .................................................................................... 107 4.6. Conclusion ........................................................................................................... 112 References ......................................................................................................................... 114 Danksagung ....................................................................................................................... 129 Appendix ............................................................................................................................ 130 4.7. Appendix A ........................................................................................................... 130 4.8. Appendix B ........................................................................................................... 133 Erklärung ............................................................................................................................ 137 2 Abstract The long-lived 138La-138Ce decay system (half-life 1.02 x 1011 a) is a potentially useful tool to study the behavior of the light rare earth elements (LREE) and to unravel information about the timing of geological processes and about the interaction of geological reservoirs on Earth. In earth sciences, the 138La-138Ce geochronometer can therefore complement information from the more popular long-lived 147Sm-143Nd and 176Lu-176Hf isotope systems. This thesis presents a new analytical protocol
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