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University of Cape Coast by George Yaw Hadzi October

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University of Cape Coast by George Yaw Hadzi October UNIVERSITY OF CAPE COAST ASSESSMENT OF HEAVY METALS AND METALLOID IN SOILS, SEDIMENTS AND WATER FROM PRISTINE AND MAJOR MINING AREAS IN GHANA - DATA TO AID GEOCHEMICAL BASELINE . SETTING BY GEORGE YAW HADZI e Thesis submitted to the Department of Chemistry of the School of Physical Sciences, College of Agriculture and Natural Sciences, University of Cape Coast, in partial fulfilment of the requirements for the award of Doctor of Philosophy degree in Chemistry OCTOBER 2017 DECLARATION Candidate’s Declaration I hereby declare that this thesis is the result of my own original research and that no part of it has been presented for another degree in this university or elsewhere. Candidate’s Signature Date Name: GEORGE YAW HADZI Supervisors’ Declaration We hereby declare that the preparation and presentation of the thesis were supervised in accordance with the guidelines on supervision of thesis laid down by the University of Cape Coast Principal Supervisor’s Signature Dtae Name: PROF. DAVID KOFI ESSUMANG Co-Supervisor’s Signature ..Q? Name: PROF. SHILOH KWABENA DEDEH OSAE ii 4;^ JONAH LIBRARY OF CAPE COAST ABSTRACT The distribution, risks and geochemical baseline analysis of the heavy metals in soils, sediments and water in pristine and major mining areas in Ghana were investigated. The surface soils, sediment and water were pulverized, acid digested, and analyzed for the major and minor elements using (ICP- QQQMS). The average metals and metalloid (As, Cd, Pb and Zn) concentrations from the mining sites were higher than the pristine sites (p>0.05) with many of the metals not detected in pristine water samples. The natural geogenic metals however, showed varied concentrations in both the pristine and the mining areas. The total heavy metals concentrations from the study ranged from 0.OHO.01 (Cd) to 86859.36±47.07 (Fe) in the soils and sediments and 0.002±0.00 (As) to 0.929±0.06 mg/L (Fe) in the waters. With the exception of Al, Fe, Mn and As, the metals levels in the water samples were generally found to be below the WHO, EC and USEPA guideline limits. For the soils and sediments, the concentrations of Cd, Pb and Zn were below the guideline limits. However, As showed exceptionally high concentrations in samples from the mining areas, especially those from Obuasi and Kwabeng mining areas, indicating a potential biological effects. Elevated human health risk indices (>10“4) were obtained for As and Cr with the severity of the metals and metalloid in the soils and sediment ranked as As >Cr> Pb> Cd. The multi-criteria ranking, employing PROMETHEE and GAIA, indicated that the pristine sites have low degree of contamination which is suitable for setting the geochemical baseline values for the metals and metalloid in the pristine areas. The proposed geochemical baseline values will be applied for speedy identification of sites that could be affected by heavy metals contamination. iii KEY WORDS Contamination Geochemical baseline Health risk Heavy Metals Mining Pristine iv ACKNOWLEDGEMENTS First and foremost, I would like to express my gratitude to my two supervisors; Prof. D. K. Essumang and Prof. Shiloh K. D. Osae for their patience, guidance and invaluable contributions in all aspects of this Thesis Work and whose supervisory style was central to the completion of this research: I would like to especially thank Prof. Godwin Ayoko of Queensland University of Technology (QUT) - Australia for accepting my candidature and providing me with excellent supervisory support throughout my sample analysis. Furthermore, my sincere gratitude goes to Karren, Sunny, Shane, Aarshi, Irina, James and David of the Central Analytical Research Facility (CARF) of QUT for the provision of resources and immense support for this project. Access to CARF was supported by generous funding from QUT’s Science and Engineering Faculty (SEF). I am very thankful to some PhD students of QUT; Alfred, Godfred, Mawutorli and Gustav for their contributions towards this work. I must not also forget my very good friend Kwabena who volunteered as my escort to all the forest reserves and other sampling sites. My sincere thank also goes to the University of Cape Coast and the Government of Ghana for granting me financial assistance in every facets of this project and not forgetting Mr Agyemang of Agric Technology Center. To my brothers and sisters for your interest and inputs in my life and this work has been invaluable to my educational success. Finally, I thank the lecturers and colleague Teaching Associates (TAs) and the entire staff of Department of Chemistry, for their diverse contributions towards this project. Thank you for everything, everyone. v DEDICATION To my lovely mother, Christine Afiia Asamoah and my beautiful wife, Noelle Ablah Nazzar vi TABLE OF CONTENTS Page DECLARATION ii ABSTRACT iii KEY WORDS iv ACKNOWLEDGEMENTS v DEDICATION vi TABLE OF CONTENTS Vll LIST OF TABLES xvi LIST OF FIGURES xxn LIST OF ACRONYMS XXVI CHAPTER ONE: INTRODUCTION Background to the Study 1 Statement of the Problem 7 Objectives for the Study 10 General Objective 10 Specific Objectives 11 Justification 11 Hypotheses for the Study 15 Organization of the Study 16 Chapter Summary 17 CHAPTER TWO: LITERATURE REVIEW Introduction 19 Sources and Distribution of Heavy Metals 20 Mining Processes and Industrial Wastes 24 Pesticides 25 vii Heavy Metals Occurrence and Health Effects 25 Mercury 26 Lead 28 Arsenic 30 Chemical and Physical Properties of Soil and Sediment 32 Cation Exchange Capacity Application and Principle 33 Exchangeable Cations and Cation Exchange Capacity (CEC) 34 Determination of Cation Exchange Capacity 34 Effect of pH and CEC on Metal Mobility 36 Effect of Organic Matter on Heavy Metals Availability 37 Adsorption, Complexation and Chelation of Metals to Organic Matter 38 Acid Mine Drainage 38 Biological Importance of Heavy Metals 40 Health Risks of Heavy Hetals 41 Mechanism of Heavy Metals Toxicity 42 Background of Heavy Metals in Risk Assessment 46 Bioavailability 46 Susceptible Populations 48 Demographics 48 Concurrent Damage or Disease 49 Human Health Risk Assessment 49 Hazard Identification 50 Dose-response 50 Exposure Assessment 51 Dermal Exposure 53 viii Heavy Metals Conceptual Model 53 Risk Characterization 54 Gold Mining and the State of Heavy Metals pollution in Ghana 56 History 56 Impact of Gold Mining and Heavy Metal Pollution 57 Heavy Metal Pollution and Cancer 60 Methods for Determination of Metals in Soils, Sediments and Water 61 Exchangeable Fraction 64 The Carbonate Fraction 65 The Reducible Fraction 65 The Organic and Sulphide Fraction 66 Residual Fraction 67 Mining activities and Heavy Metals Quality Guidelines in Ghana 68 Geochemical Background and Baseline Values Determination 69 Integrated Method for Geochemical Background Determination 71 Pollution Indices for Assessing Sediment Contamination by Heavy Metals 72 Modified Degree of Contamination and Modified Pollution Index 73 Modified Ecological Risk Index (MR1) 75 Multivariate Techniques in Soil/Sediment Assessment 77 Pearson Correlation Coefficients 77 PCA/HCA Analysis 78 Multicriteria Technique for Ranking Metals at the Sampling Sites 79 PROMETHEE and GAIA 79 ICP-MS Analysis 80 The Principle 80 ix Analysis of Heavy Metals with ICP/MS 82 Chapter Summary 83 CHAPTER THREE: METHODOLOGY Introduction 84 Study Area Description 85 Physiography and Selection of the Study Area 86 Sampling Plan 88 Field Methods 89 Siol and Sediment Sample Collection 89 Soil and Sediment Sample Preparation 90 Water Sample collection and Treatment 92 Centrifuge tubes and Glassware Cleaning Process 92 Measurement of Soil and Sediment Particle Size 93 pH and EC Determination of Soil, Dater and Dediment Samples 95 Soil and Sediment Organic Carbon Determination 96 Determination of Cation Exchange Capacity 97 Digestion and Analysis of Water samples 98 Physico-chemical Analysis of Water 98 Digestion and Analysis of Soil and Sediment Samples 100 Weak Acid Extractable Metals 100 Total Recoverable Metal Analysis (aqua regia digestion) 100 Reagents 101 Quality Control (QC) 101 Recovery and Reproducibility 103 Reagents and Standards 103 x Reference Sample Preparation for ICP-MS Analysis 103 ICP-MS Analysis 104 Data and Statistical Analysis 105 PROMETHEE and GAIA 105 Assessment of Heavy Metal Contamination 106 Contamination Factor 106 Enrichment Factors 107 Index of Geo-accumulation 108 Modified Pollution Index 109 Ecological Risk Assessment 109 Modified Ecological Risk Index 109 Questionnaire and statistical analyses 110 Human Health Risk Assessment 111 Chapter Summary 114 CHAPTER FOUR: RESULTS AND DISCUSSION Introduction 115 Heavy Metal Levels and Distribution in the Soils, Sediments and Water 116 Quality Control Results 116 Accuracy and Precision/Reproducibility 118 Soil Textural Class 119 Physicochemical Characteristics of the Soils 120 Physico-chemical Characteristics of the Sediment 123 Physico-chemical Characteristics of the Water Samples 125 Concentration of Heavy Metals in Water from the Pristine and Mining areas 128 xi Heavy Metals Concentration in Sediments (aqua regia digestion) 139 Concentrations of the Metals in Soils with 1.0M HNO3 144 Heavy Metal Concentrations in Soils by Aqua Regia 150 Statistical Analysis of Heavy Metals in Soils and Sediments Water 157 Statistical analysis of metals in the water samples 157 PROMETHEE and GALA Analysis of the Metals in Sediment 160 Statistical Analysis of Heavy Metals in the River Sediment 162 PROMETHEE and GAIA Analysis of the Heavy Metals in Sediments 167 Statistical Analysis of Heavy Metals
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