Microscopic, chemical and spectroscopic investigations on emeralds of various origins Dissertation zur Erlangung des Grades „Doktor der Naturwissenschaften“ am Fachbereich Chemie, Pharmazie und Geowissenschaften der Johannes Gutenberg-Universität Mainz Le Thi Thu Huong geb. in Thanh Hoa, Vietnam Mainz, 2008 Dekan: 1. Berichterstatter: 2. Berichterstatter: Tag der mündlichen Prüfung: Hereby I declare that I have written the present doctoral thesis on my own and without any illegal help. All literature sources are indicated. Mainz, April 2008 --------------------------- Contents CONTENTS CONTENTS ------------------------------------------------------------------------------------------------------------------------i INDEX OF FIGURES------------------------------------------------------------------------------------------------------------ iii INDEX OF TABLES------------------------------------------------------------------------------------------------------------- vii ABBREVIATIONS --------------------------------------------------------------------------------------------------------------viii ACKNOWLEDGEMENT ------------------------------------------------------------------------------------------------------ ix ABSTRACT ------------------------------------------------------------------------------------------------------------------------x ZUSAMMENFASSUNG-------------------------------------------------------------------------------------------------------- xi 1. INTRODUCTION AND OBJECTIVES ----------------------------------------------------------------------------------- 1 1.1. THE CRYSTAL STRUCTURE OF BERYL -------------------------------------------------------------------------- 1 1.2. POSSIBILITIES TO DETERMINE ORIGINS OF EMERALDS AND SEPARATION BETWEEN NATURAL EMERALDS FROM SYNTHETIC ONES – STATE OF THE ART STUDY AND RESULTS OF THE PRESENT THESIS------------------------------------------------------------------------------------------------------------------------ 4 2. SHORT DESCRIPTION OF SAMPLES AND ORIGINS------------------------------------------------------------- 10 2.1. NATURAL EMERALDS ------------------------------------------------------------------------------------------ 10 Colombia --------------------------------------------------------------------------------------------------------- 10 Brazil ---------------------------------------------------------------------------------------------------------------- 11 Austria ------------------------------------------------------------------------------------------------------------- 14 Russia --------------------------------------------------------------------------------------------------------------- 15 Zambia ------------------------------------------------------------------------------------------------------------ 16 South Africa ------------------------------------------------------------------------------------------------------ 16 China -------------------------------------------------------------------------------------------------------------- 16 Nigeria ------------------------------------------------------------------------------------------------------------- 17 Madagascar ---------------------------------------------------------------------------------------------------- 17 Classification of the emerald deposits ----------------------------------------------------------------- 18 2.2. SYNTHETIC EMERALDS ----------------------------------------------------------------------------------------- 18 2.2.1. Flux-grown synthesis ---------------------------------------------------------------------------------- 19 2.2.2. Hydrothermally-grown synthesis ------------------------------------------------------------------ 20 3. INCLUSIONS -------------------------------------------------------------------------------------------------------------- 22 3.1. Chivor (Colombia) -------------------------------------------------------------------------------------------- 22 3.2. Santa Terezinha (Brazil) -------------------------------------------------------------------------------------- 25 3.3. Socoto (Brazil) --------------------------------------------------------------------------------------------------- 27 3.4. Carnaiba (Barzil) ----------------------------------------------------------------------------------------------- 30 3.5. Capoeirana (Brazil) ------------------------------------------------------------------------------------------- 31 3.6. Itabira (Brazil) ---------------------------------------------------------------------------------------------------- 32 3.7. Manajary (Madagascar) ----------------------------------------------------------------------------------- 34 3.8. Habachtal (Austria) ------------------------------------------------------------------------------------------- 37 3.9. Kafubu (Zambia) ----------------------------------------------------------------------------------------------- 38 3.10. Gwantu (Nigeria) -------------------------------------------------------------------------------------------- 40 3.11. Transvaal (South Africa) ----------------------------------------------------------------------------------- 41 3.12. Ural (Russia) ---------------------------------------------------------------------------------------------------- 42 3.13. Malipo (China) ------------------------------------------------------------------------------------------------ 44 3.14. Flux-grown syntheses ---------------------------------------------------------------------------------------- 45 3.15. Hydrothermally-grown syntheses ----------------------------------------------------------------------- 47 Discussion -------------------------------------------------------------------------------------------------------------- 48 i Contents 4. CHEMICAL PROPERTIES OF INVESTIGATED EMERALDS ----------------------------------------------------- 52 4.1. Silicon (Si) -------------------------------------------------------------------------------------------------------- 54 4.2. Aluminium (Al) ------------------------------------------------------------------------------------------------- 55 4.3. Beryllium (Be) --------------------------------------------------------------------------------------------------- 55 4.4. Lithium (Li) ------------------------------------------------------------------------------------------------------- 56 4.5. Sodium (Na) ---------------------------------------------------------------------------------------------------- 57 4.6. Magnesium ((Mg) --------------------------------------------------------------------------------------------- 58 4.7. Gallium (Ga) ---------------------------------------------------------------------------------------------------- 58 4.8. Caesium (Cs) --------------------------------------------------------------------------------------------------- 58 4.9. Iron (Fe) ----------------------------------------------------------------------------------------------------------- 59 4.10. Niobium (Nb) and Strontium (Sr) ----------------------------------------------------------------------- 59 4.11. Titanium (Ti) ---------------------------------------------------------------------------------------------------- 60 4.12. Nickel (Ni) ------------------------------------------------------------------------------------------------------ 60 4.13. Rubidium (Rb) ------------------------------------------------------------------------------------------------ 60 4.14. Vanadium (V) ------------------------------------------------------------------------------------------------ 61 4.15. Molybdenum (Mo) ------------------------------------------------------------------------------------------ 61 4.16. Potassium (K) -------------------------------------------------------------------------------------------------- 62 4.17. Manganese (Mn) -------------------------------------------------------------------------------------------- 62 4.18. Chromium (Cr) ----------------------------------------------------------------------------------------------- 63 4.19. Scandium (Sc) ------------------------------------------------------------------------------------------------ 63 Discussion -------------------------------------------------------------------------------------------------------------- 64 5. RAMAN MICRO-SPECTROSCOPY OF EMERALDS ------------------------------------------------------------- 67 5.1. Raman spectra in the range from 200 cm-1 to 1600 cm-1 -------------------------------------- 68 5.1.1. Comparisons of Raman spectra up to 1600 cm-1 of emeralds from various deposits ---------------------------------------------------------------------------------------------------------- 69 5.1.2. Bands around 1067-1072 cm-1 ------------------------------------------------------------------- 73 5.2. Raman spectra of emeralds at high Raman shift: 3500-3700 cm-1 -------------------------- 77 5.2.1. Measurements under room temperature --------------------------------------------------- 77 5.2.2. Measurements under low temperatures ----------------------------------------------------- 80 6. INFRARED SPECTROSCOPY OF EMERALDS --------------------------------------------------------------------- 86 6.1. IR absorption spectroscopy in the range 400-1500 cm-1 --------------------------------------- 89 6.2. IR absorption spectroscopy in the ranges 1500-1700 cm-1 and 3300-3800 cm-1 -------- 98 CONCLUSIONS -------------------------------------------------------------------------------------------------------------- 102 REFERENCES ---------------------------------------------------------------------------------------------