DETERMINATION OF SOME TRACE METALS IN ELSARAF DAM (GEDAREF) By Tayser Ismail Yagoob A thesis submitted in fulfillment of the requirement for the degree of Master of Science (Chemistry) in the University of Khartoum Department of Chemistry Faculty of Science University of Khartoum, Sudan July 2001 LIST OF CONTENTS page List of Tables iv List of Figures vi Acknowledgment ix Abstract ( in Arabic) x Abstract (in English) xi CHAPTER ONE 1.Introduction 1 1.1 Trace elements. 1 1.1.1. Classification of trace elements. 1 1.1.1.1. Essential trace elements. 2 1.1.1.2. Non essential trace elements. 3 1.1.1.3. Toxic trace elements. 3 1.1.2 Trace elements in living organisms. 3 1.1.3. Trace elements in soils. 4 1.1.4.Trace elements in water. 5 1.1.5.Trace elements in plant. 6 1.1.6. Biological role of trace elements. 7 1.1.7. Individual nutrients. 9 1.1.7.1. Iron. 9 1.1.7.2. Manganese. 10 1.1.7.3. Copper. 12 1.1.7.4. Cobalt. 14 1.1.7.5. Nickel. 14 1.1.7.6. Zinc. 15 1.1.8 Individual pollutants 16 1.1.8.1 Cadmium. 16 1.1.8.2 Chromium. 18 1.2. Atomic spectroscopy. 20 1.2.1 Theory of atomic spectroscopy. 20 1.2.2. Flame atomization. 21 1.2.3. Instruments. 24 1.2.4. Theory of atomic absorption spectroscopy. 24 1.3. X-ray fluorescence methods. 25 1.3.1. Principles. 26 1.3.2. Instruments. 27 1.3.3. Wavelength dispersive instruments. 27 1.3.4. Energy dispersive instruments. 28 1.3.5. Nondispersive instruments. 29 1.3.6. Advantages and disadvantages of X-ray 30 fluorescence method. 1.4. Metal ions preconcentration. 31 1.4.1. Chelation and solvent extraction. 32 1.4.2. Dithiocarbamate extraction method. 33 1.4.3. 8-hydroxyquinoline (oxine). 35 Research objective 37 CHAPTRTWO 2. EXPERIMENTAL 2.1. Instruments. 38 2.2.Chemicals. 38 2.3. Samples collections. 38 2.4. AAS. Measurements. 39 2.4.1. Sample preparations. 39 2.4.1.1. Plantand soil samples. 39 2.4.1.2. Water samples. 40 2.4.1.2.1. Oxine extraction procedure. 40 2.4.1.2.2. APDC-MIBK extraction procedure. 40 2.4.2. Preparations of standards. 41 2.4.3. Calibration. 42 2.5. X-ray fluorescence. 42 2.5.1. Samples treatments and XRF measurements. 42 CHAPTRE THREE 3. DISCUSSION. 81 REFERENCES. 84 LIST OF TABLES page Table 1. Iron concentration (ppm) for soil and plant (first 43 season) Table 2. Copper concentration (ppm) for soil and plant 43 (first season) Table 3. Cobalt concentration (ppm) for soil and plant 44 (first season) Table 4 Manganese concentration (ppm) for soil and plant 44 (first season) Table 5. Chromium concentration (ppm) for soil and plant 45 (first season) Table 6. Nickel concentration (ppm) for soil and plant 45 (first season) Table 7. Cadmium concentration (ppm) for soil and plant 46 (first season) Table 8. Zinc concentration (ppm) for soil and plant (first 46 season) Table 9. Iron concentration (ppm) for soil and plant 47 (second season) Table 10. Copper concentration (ppm) for soil and plant 47 (second season) Table 11. Cobalt concentration (ppm) for soil and plant 48 (second season) Table 12. Manganese concentration (ppm) for soil and 48 plant (second season) Table 13. Chromium concentration (ppm) for soil and 49 plant (second season) Table 14. Nickel concentration (ppm) for soil and plant 49 (second season) Table 15. Cadmium concentration (ppm) for soil and plant 50 (second season) Table 16. Zinc concentration (ppm) for soil and plant 50 (second season) Table 17. Comparison of the AAS results obtained with 51 the certified values for the CRM of soil-7. Table 18. Comparison of the AAS results obtained with 51 the certified values for the CRM of hay powder. Table 19. Water metal ions concentration (ppm) using 52 oxine (first season): Table 20. Water metal ions concentration (ppm) using 53 oxine (2nd season): Table 21. Water metal ions concentration (ppm) using 54 APDC (2nd season): Table 22. Efficiency of oxine (pH 6.5) 55 Table 23. Efficiency of APDC (pH 4) 56 Table 24. Botanical and common names of the plants 77 investigated. Table 25. Location of the sites for water samples. 80 LIST OF FIGURES Page Fig. 1. XRF and AAS concentrations of iron for the first season 57 (soil). Fig. 2. XRF and AAS concentrations of copper for the first season 57 (soil). Fig. 3. XRF and AAS concentrations of cobalt for the first season 58 (soil). Fig. 4. XRF and AAS concentrations of manganese for the first 58 season (soil). Fig. 5. XRF and AAS concentrations of chromium for the first 59 season (soil). Fig. 6. XRF and AAS concentrations of nickel for the first season 59 (soil). Fig. 7. XRF and AAS concentrations of iron for the first season 60 (plant). Fig. 8. XRF and AAS concentrations of copper for the first season 60 (plant). Fig. 9. XRF and AAS concentrations of cobalt for the first season 61 (plant). Fig. 10. XRF and AAS concentrations of manganese for the first 61 season (plant). Fig. 11. XRF and AAS concentrations of chromium for the first 62 season (plant). Fig. 12. XRF and AAS concentrations of nickel for the first 62 season (plant). Fig. 13. Concentrations of iron for the first and second season in 63 the soil using AAS. Fig. 14. Concentrations of copper for the first and second season 63 in the soil using AAS. Fig. 15. Concentrations of cobalt for the first and second season 64 in the soil using AAS. Fig. 16. Concentrations of manganese for the first and second 64 season in the soil using AAS. Fig. 17. Concentrations of chromium for the first and second 65 season in the soil using AAS. Fig. 18. Concentrations of nickel for the first and second season 65 in the soil using AAS. Fig. 19. Concentrations of cadmium for the first and second 66 season in the soil using AAS. Fig. 20. Concentrations of zinc for the first and second season in 66 the soil using AAS. Fig. 21. Concentrations of iron for the first and second season in 67 the plant using AAS. Fig. 22. Concentrations of copper for the first and second season 67 in the plant using AAS. Fig. 23. Concentrations of cobalt for the first and second season 68 in the plant using AAS. Fig. 24. Concentrations of manganese for the first and second 68 season in the plant using AAS. Fig. 25. Concentrations of chromium for the first and second 69 season in the plant using AAS. Fig. 26. Concentrations of nickel for the first and second season 69 in the plant using AAS. Fig. 27. Concentrations of cadmium for the first and second 70 season in the plant using AAS. Fig. 28. Concentrations of zinc for the first and second season in 70 the plant using AAS. Fig. 29. Concentration of iron for the first and second season in 71 the water using oxine. Fig. 30. Concentration of copper for the first and second season in 71 the water using oxine. Fig. 31. Concentration of cobalt for the first and second season in 72 the water using oxine. Fig. 32. Concentration of manganese for the first and second 72 season in the water using oxine. Fig. 33. Concentration of chromium for the first and second 73 season in the water using oxine. Fig. 34. Concentration of nickel for the first and second season in 73 the water using oxine. Fig. 35. Extraction efficiency for iron using APDC and Oxine. 74 Fig. 36. Extraction efficiency for copper using APDC and Oxine. 74 Fig. 37. Extraction efficiency for cobalt using APDC and Oxine. 75 Fig. 38. Extraction efficiency for manganese using APDC and 75 Oxine. Fig. 39. Extraction efficiency for chromium using APDC and 76 Oxine. Fig. 40. Extraction efficiency for nickel using APDC and Oxine. 76 Fig. 41. Extraction efficiency for zinc using APDC and Oxine. 77 Fig. 42. Concentrations of some trace elements in water samples 78 using Oxine (first season). Fig. 43. Concentrations of some trace elements in water samples 79 using Oxine (second season). ACKNOWLEDGMENT Firstly, praise be to Allah. My appreciation and gratitude, to my honourable supervisor Dr. Taj Elsir Abbas Ahmed, for his continuous support. encouragement, valuable counsel, patience and guidance to finish this work. I am greatly indebted to Dr. Mohamed Ahmed Hassan Eltayeb (Sudan Atomic Energy Commission) [SAEC], for his invaluable assistance and directions throughout the work. My appreciation extends to the statTof Urban Water Authority (Gedareff State), for their help, financial support and facilities in sample collection. I woud like to express my thanks to the staff of Geological and Reseach Authority of The Sudan (Chemistry Laboratory), for allowing me to use the laboratory facilities . At last and not least, I wish to express my deepest gratitude to my friends and all statTof Chemistry Department, University of Khartoum for their assistance, the fruit and pleasure time I spend with them. .• -j' '-«" AJV JJ ^-ij J ^' :— ^—J T . *. • •!j^- - ^ • ^ -' ^ • '' r j - •*•' ^JLJ ^jj - -j - ^i '^ '-j-^ •*•- jjliiAll ^;-j » Ajt^VI . ..L J^ja. ^^.'.. I LailJ Ajjjll j ^lLlj]l J 6LJ CJUJC JjLkjl (AAS) . J^W^AII ^£ ^ OUjil j Ajjjil CJUJC ^_|n:v Jj^'^ (XRF) «ui ^J ij^i ^uyii JJSJ; j^, «xai ji^y Ujd =i» ^.^i I Ui ^i JSJI fi Jjivull •Ui (36800/33580 ,56600/54900) LJIj ^Gbill AJU U% ^UJJVI j^.L^L.7 AJLU ^ULO« JJSI jlS Sj^JI ^U; Amin niium pyrrolidinc dithiocarbamate j 8-hydroxyquinolinc.