vii TABLE OF CONTENT CHAPTER TITLE PAGE DECLARATION ........................................................................... ii DEDICATION ........................................................... iii ACKNOWLEDGEMENT............................................................. v ABSTRACT ........................................... vi ABSTRAK .................................................................................... vii TABLE OF CONTENTS ..................................................... viii LIST OF TABLES ....................................................................... xii LIST OF FIGURES .................................................................... xiv LIST OF GLOSSARY .............................................................. xviii 1 INTRODUCTION ......................................................................... 1 1.1 Background ..................................................................................... 1 1.2 Statement of the Problem .................................................................. 4 1.3 Objectives ......................................................................................... 5 1.4 Significance of the Study .................................................................. 5 1.5 Scope of the Study ............................................................................ 5 1.6 Outline of the Thesis ......................................................................... 6 viii 2 LITERATURE REVIEW ............................................................. 7 2.1 Introduction ....................................................................................... 7 2.2 Definition of Heavy Metals ............................................................... 8 2.3 Sources of Heavy Metals in the Environment .................................. 9 2.4 Pollution ......................................................................................... 13 2.5 Toxicity of Heavy Metals................................................................ 15 2.6 Impact of Heavy Metals on the Environment ................................. 16 2.6.1 Heavy Metals Impact On Water .......................................... 16 2.6.2 Heavy Metals Impact On Soil and Plant ............................ 17 2.7 Effect of Heavy Metals on Animal Health ...................................... 19 2.8 Effect of Heavy Metals on Human Health ...................................... 20 2.9 Sorghum and Alfalfa ...................................................................... 22 2.10 Sources and Status of Water in Oman ............................................ 23 2.11 Heavy Metals Analysis ................................................................... 24 2.11.1 Atomic Absorption Spectrometry.................................. .....24 2.11.2 Inductively Coupled Plasma Spectrometry ......................... 27 2.12 Monitoring of Heavy Metals ......................................................... 32 3 EXPERIMENTAL ....................................................................... 36 3.1 Chemicals and Reagents ................................................................. 36 3.2 Instruments and Apparatus ............................................................. 36 3.3 Sampling Area................................................................................. 37 3.4 Sample collection ............................................................................ 37 3.4.1 Collection of Water Samples .............................................. 44 3.4.2 Collection of Soil Samples .................................................. 44 3.4.3 Collection of Plant Samples ................................................. 44 3.5 Extraction Procedure for the Soil Sample ...................................... 44 ix 3.6 Digestion Procedure for the Plant Sample ..................................... 45 3.7 Preparation of Standards and QCs Solutions ................................. 45 3.8 Sample Analysis .............................................................................. 47 3.8.1 pH of Water and Soil Samples ........................................... 47 3.8.2 Electric Conductivity (EC) of Soil...................................... 48 3.8.3 Total Nitrogen (N) of Soil .................................................. 48 3.8.4 Heavy Metals of Water, Plant and Soil............................... 48 3.9 Data Analysis .................................................................................. 49 4 RESULTS AND DISCUSSION .................................................. 50 4.1 Sampling Sites 4.2 Soil Taxonomy …..50 ……………………………………………... 52 4.3 pH and Electrical Conductivity (EC) and Total Nitrogen Values .. 56 4.4 Concentration of Heavy Metals in Soil ........................................... 59 4.4.1 Variation of Heavy Metal Content in 20 Farms ................ 59 4.4.2 Overall Mean Concentration of Heavy Metal in Four ........... Regions .............................................................................. 62 4.5 Concentration of Heavy Metals in Plant ......................................... 67 4.5.1 Variation of Heavy Metal Content in 20 Farms ................ 67 4.5.2 Overall Mean Concentration of Heavy Metal in Four ........... Regions in Plant ................................................................. 71 4.5.3 AAS Analysis of Heavy Metals in Plant ............................ 74 4.6 pH and EC of in Well Water ......................................................... 75 4.7 Concentration of Heavy Metals in Well Water ............................... 77 4.7.1 Variation of Heavy Metal Content in 20 Farms .................. 77 4.7.2 Overall Mean Concentration of Heavy Metal in Four ............. Regions .............................................................................. 80 x 4.8 4.9 5 Correlation between Concentration of Nickel in Soil, Plant and Water Samples 85 Proposed Maximum Permissible Level of Heavy Metals in Omani Soil and Well Water 87 CONCLUSION AND FUTURE WORK .................................... 89 5.1 Conclusions ............................................................................. 89 5.2 Future Work 91 REFERENCES ...................................................................................... 92 Appendix A-M 100 - 112 xi LIST OF TABLES TABLE NO. TITLE PAGE 2.1 Water balance in million cubic metres per year 24 2.2 Comparison between ICP-OES, FAAS and GAAS. 32 2.3 Maximum permissible levels of selected heavy metals in water, 33 soil and plant samples. 3.1 Latitude and Longitude coordinates of twenty farms selected for the determination of levels of heavy metals in water, soil and plant. 3.2 Calibration Standards (STD) concentrations of element under study for ICP-OES 3.3 53 The pH, EC and total N range in soil samples of four regions in the Sultanate of Oman 4.3 47 Taxonomy of soil of the selected farms (n=20) sampled for the determination of heavy metal contents in water, soil and plants. 4.2 46 Calibration Standards (STD) concentrations of Cd, Cu, Cr, Mn, and Zn for AAS. 4.1 38 57 Comparison of mean heavy metal concentrations (µg/g) between Batinah North, Batinah South, Dakhliah and Sharqiah regions in the Sultanate of Oman. 4.4 The mean concentration of heavy metals of plant of four 66 72 xii regions in the Sultanate of Oman 4.5 Concentrations of Cd, Cu, Mn, and Zn in plant samples using AAS 4.6 74 The pH and EC values in water samples of four regions in the Sultanate of Oman 4.7 Classification of saline waters 4.8 Comparison of mean heavy metal concentrations in water 76 76 between Batinah North, Batinah South, Dakhiliyah and Sharqiyah regions in the Sultanate of Oman 4.9 84 Proposed maximum permissible level of heavy metals in saoil and water in the Sultanate of Oman 88 xiii LIST OF FIGURES FIGURE NO. 2.1 TITLE PAGE The relationship between health effect and the amount of elements, for (a) Essential elements, and (b) toxic elements 2.2 16 The soil-plant system showing the key components relating to the dynamics of heavy metals 18 2.3 Photographs of a) Sorghum and b) Alfalfa 22 2.4 Schematic diagram of (a) Graphite furnace and (b) Flame burner 25 2.5 Schematic diagram of A hollow cathode lamp 26 2.6 Schematic diagram of flame atomic absorption spectrometry 27 2.7 Schematic diagram of Inductively Coupled Plasma- Optical Emission spectrometry (ICP-OES) 28 2.8 Schematic diagram of Nebulizer 29 2.9 Schematic diagram of a typical ICP source called torch. Position A shows radial viewing of the torch. 30 2.10 Temperature in typical ICP source 31 3.1 Map showing the locations of the four selected regions of Oman sampled for measuring the heavy metal contents of 39 xiv water, soil and plants. 3.2 Map showing the locations of 5 selected farms selected from Batinah North (BN) region of Oman sampled for measuring the heavy metal contents of water, soil and plants. 3.3 40 Map showing the locations of 5 selected farms selected from Batinah South (BS) region of Oman sampled for measuring the heavy metal contents of water, soil and plants. 3.4 41 Map showing the locations of 5 selected farms selected from Dakhiliyah (DH) region of Oman sampled for measuring the heavy metal contents of water, soil and plants. 3.5 42 Map showing the locations of 5 selected farms selected from Sharqiah (SH) region of Oman sampled for measuring the heavy metal contents of water, soil and plants. 4.1 Map of Oman showing the sampling regions. Inset showing economic activity of the related sampling regions 4.2 43 51 Satellite map showing the locations of 5 selected farms each from Batinah North & South regions of Oman sampled for measuring the heavy metal contents of soil. 4.3 54 Satellite map showing the locations of 5 selected farms each from Sharqiyah & Dakhiliyah regions of Oman sampled for measuring the heavy metal contents of soil 4.4 55 The concentration of heavy metals in soil (µg/g) of Batinah North and South regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.5 60 The concentration of heavy metals in soil (µg/g) of Dakhiliyah & Sharqiyah regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.6 61 The overall mean level of heavy metals in soil (µg/g) of four regions in The Sultanate of Oman during November, 2009 to 63 xv July, 2010. 4.7 The concentration of heavy metals in soil (µg/g) of four regions in The Sultanate of Oman during November, 2009 to July, 2010 64 4.8 The concentration of Cd, Co, Cu and Cr in soil (µg/g) of 20 farms in The Sultanate of Oman during November, 2009 to July, 2010. 4.9 68 The concentration of Fe, Pb, Mn and Mo in plant (µg/g) of 20 farms in The Sultanate of Oman during November, 2009 to July, 2010 4.10 69 The concentration of Ni, V and Zn in plant (µg/g) of 20 farms in The Sultanate of Oman during November, 2009 to July, 2010. 4.11 70 The overall mean level of heavy metals in plant (µg/g) of four regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.12 73 The concentration of heavy metals in plant (µg/g) of four regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.13 73 The concentration of heavy metals in water (mg/L) of (a) Batinah North and (b) Batinah South regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.14 78 The concentration of heavy metals in water (mg/L) of (a) Dakhiliyah and (b) Sharqiyah regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.15 The overall mean level of heavy metals in water (mg/L) of four 79 81 xvi regions in The Sultanate of Oman during November, 2009 to June, 2011. 4.16 The concentration of heavy metals in water (mg/L) of four sampling in The Sultanate of Oman during November, 2009 to June, 2011. 4.17 82 Concentration of heavy metals in water (mg/L) of four regions in The Sultanate of Oman during November, 2009 to July, 2010. 4.18 83 Correlations of plots of concentration of Ni (a) in soil and plant (b) in soil and water and (c) in plant and water 86 xvii LIST OF GLOSSARY AAS Atomic Absorption Spectrometry FAAS Flame Atomic Absorption Spectrophotometer GPS Global Positioning System. GFAAS Graphite Atomic Absorption Spectrophotometer ICP-OES Inductively Coupled Plasma- Optical Emission spectrometry. PTWIs Provisional Tolerable Weekly Intakes PMTDIs Provisional Maximum Tolerable Daily Intakes JECFA Joint Expert Committee on Food Additives FAO Food and Agriculture Organization MPL Maximum Permissible Level TN Total Nitrogen USEPA United State Environmental Protection Agency WHO World Health Organization
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