ENVIRONMENTAL GEOCHEMISTRY OF ATTOCK AND HARIPUR BASINS, PAKISTAN BY SHAZIA JABEEN NATIONAL CENTRE OF EXCELLENCE IN GEOLOGY UNIVERSITY OF PESHAWAR PAKISTAN 2013 ENVIRONMENTAL GEOCHEMISTRY OF ATTOCK AND HARIPUR BASINS, PAKISTAN A MANUSCRIPT PRESENTED TO THE NATIONAL CENTRE OF EXCELLENCE IN GEOLOGY, UNIVERSITY OF PESHAWAR IN THE PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN ENVIRONMENTAL GEOSCIENCES BY SHAZIA JABEEN NATIONAL CENTRE OF EXCELLENCE IN GEOLOGY UNIVERSITY OF PESHAWAR PAKISTAN 2013 IN THE NAME OF ALLAH, MOST COMPASSIONATE, EVER MERCIFUL ACKNOWLEDGEMENTS “In the name of Allah the most merciful and beneficent” All prayers for Almighty Allah, the most merciful and beneficent, without Whose consent and consecration nothing would ever be imaginable. I am absolutely beholden by my Lord’s generosity in this effort. Praises be to Holy Prophet for He is a beacon as I pace on in my life and work. First of all I want to acknowledge my supervisor Dr. Mohammad Tahir Shah, Professor, National Centre of Excellence in Geology, University of Peshawar, Pakistan without whom I may have not been able to compile this research thesis than I am indebted to co-supervisor Dr. Sardar Khan, Associate Professor, Department of Environmental Sciences, University of Peshawar, Pakistan for his kind support during the entire period of my PhD. I like to gratitude my foreign supervisor Dr. Andrew Meharg, Professor, Department of Soil and Environmental Sciences, Institute of Biological Sciences, University of Aberdeen, United Kingdom for his help in completing ICPMS work for my thesis. I am thankful to external evaluators and internal viva examiners for their kind suggestions to improve the quality of research presented in this thesis. Thanks are also due to Professor Dr. M. Asif Khan, Director, National Centre of Excellence in Geology, University of Peshawar, Peshawar, Pakistan for facilitating the research work during entire period of my PhD program. My gratitude goes to Dr. Tazeem Khan, Dr. Rubina Bilques, Dr. Samina Sadique, Dr. Fazal-i-Rabi, Mrs Seemi and Mrs Farhi Sahar, whose moral support always boosted my energies. Special thanks are to Mr. Muhammad Tariq (Lab technician) and Mr. Bilal (Lab Attendant) for their cooperation during entire laboratory work. I am highly obliged to my teachers and colleagues of all university especially who are working in National Centre of Excellence in Geology, University of Peshawar, Pakistan who appreciated the compilation of this Thesis. I am thankful to all people of Attock and Haripur Basins for helping me during field survey, especially local community of remote villages. My sincere thanks are to all staff, scientists and professors of University of Aberdeen, United Kingdom, especially Prof. Dr. Adam Price, Prof. Dr. Angel, and Mrs. Claire Deacon for their cooperation, technical assistant and provision of laboratory facilities. I am also thankful to my brother Assistant Professor Dr. Iftikhar Ahmed, Chairman, Department of Mathematics, University of Gujrat, Pakistan for his encouragement to do such type of unique research work. My sincere thanks are for all my precious friends and colleagues (Safia Tabassum, Khalid Latif, Wajid Ali, Muhammad Ali, Azra Yaseem, Reema Fida, Humaira Fida, Humaira Gul, Shahia Khattak, Anne Marie, Zainab, Faiz, Dr. Lorna, Dr. Nimbe Ewald, Tanveer, and Gillian Kerr) for their forbearance, helpful and enjoyable company. Nevertheless, it’s the inspiration that I derived from the unconditional love, care, and prayers of my parents, in laws, husband Dr. Muhammad Qasim Hayat, Assistant Professor, Atta-ur-Rehman School of Applied Bio-Sciences (ASAB), NUST, Islamabad, Pakistan, brothers, sisters, nephews, nieces and my children (Sabaina and Mahdi Hayat) that have propelled me as far as I have triumphed. SHAZIA JABEEN D E D I C A T I O N I DEDICATED MY THESIS TO MY PARENTS, HUSBAND AND CHILDREN Table of Contents Chapters Title Page List of Tables iv List of Figures vi List of Appendices viii List of abbreviations ix Preface x Abstract xii Chapter 1 Introduction 1-15 1.1 General statement 1 1.2 Problem statement 4 1.3 Aims and objectives 5 1.4 Study area 6 1.4.1 Attock Basin 6 Drainage 8 Population and domestic water supply 8 1.4.2 Haripur Basin 8 Drainage 9 Population and domestic water supply 9 1.5 Geology of the area 9 1.5.1 Punjal- Khairabad block 10 Proterozoic formations 10 Paleozoic and Mesozoic formations 10 1.5.2 Nathia Gali-Hissartang block 10 Proterozoic formations 12 Cambrian formations 12 Mesozoic formations 12 Tertiary formations 12 1.5.3 Kala Chitta- Margalla hill block 13 Plaeocene formations 13 Cenozoic formations 13 Mesozoic formations 14 1.6 Anthropogenic activities and sources of pollution 14 Chapter 2 Material and method 16-36 2.1 Field investigation 16 2.1.1 Water sampling 16 2.1.2 Soil sampling 16 2.1.3 Plant sampling 19 2.2 Analytical Procedures 19 2.2.1 Water analysis 19 Determination of physiochemical parameters 19 Temperature 19 pH 20 Electrical conductivity 20 Total dissolve solids 20 Total hardness 20 i Determination of anions 21 Nitrate 21 Sulphate 21 Chloride 21 Carbonate and bicarbonate 21 Determination of light elements in water 22 Calcium and Magnesium 22 Sodium and Potassium 22 Determination of heavy metals in water 24 Copper 24 Iron 24 Lead 24 Zinc 26 Nickel 26 Chromium 26 Cobalt 27 Mercury and Arsenic 27 2.2.2 Soil and plant analysis 27 Preparation of soil samples 27 Pulverizing of soil samples 27 Preparation of solution of soils for major cations 28 Preparation of solution of soils for heavy and trace elements 28 Preparation of plant samples 29 Pulverizing of plant samples 29 Preparation of solution for plant samples 29 2.2.3 Determination of physical parameters in soils 29 pH 29 Electrical conductivity 30 2.2.4 Determination of major elements in soils and plant samples 30 Calcium and Magnesium 30 Sodium and Potassium 30 2.2.5 Determination of heavy and trace elements 31 Copper 31 Iron 31 Manganese 31 Lead 33 Zinc 33 Nickel 34 Chromium 34 Cobalt 34 2.2.6 ICPMS 35 Preparation of plant samples for ICPMS 35 Preparation of soil samples for ICPMS 36 Chapter 3 Literature review 37-44 Chapter 4 Water chemistry 45-88 4.1 Introduction 45 4.2 Materials and methods 47 4.2.1 Sampling and analysis 47 ii 4.2.2 Statistical analysis 47 4.2.3 Health risk assessment 50 4.3 Results 51 4.3.1 Physico-chemical variables of water 51 4.3.2 Hydrochemical facies 54 4.3.3 Light and heavy metals in water samples 55 4.3.4 Groundwater and surface water comparison 63 4.3.5 Statistical analysis 65 4.3.5.1 Inter- relationships among metals 65 4.3.5.2 Principal component analysis 72 4.3.6 Health risk assessment 76 4.4 Discussion 82 Chapter 5 Soil chemistry 89-119 5.1 Introduction 89 5.2 Materials and methods 91 5.2.1 Statistical analysis 91 5.2.2 Index of geoaccumulation 91 5.3 Results 93 5.3.1 Inter-elemental relationship 98 5.3.2 Principal component analysis 102 5.4 Discussion 106 Chapter 6 Plant chemistry 120-146 Section I Heavy metal concentration in vegetables and cereal 120 6.1 Introduction 120 6.2 Materials and methods 122 6.2.1 Transfer factor 122 6.2.2 Metal pollution index (MPI) 122 6.2.3 Health risk index (HRI) 124 6.3 Result and discussion 124 6.3.1 Plant transfer factor from soil to plant 128 6.3.2 Metal pollution index 129 6.3.3 Estimated daily intake for HMs 131 6.3.4 Health risk index of HMs 134 Section II Heavy metal concentration in medicinal herbs 136 6.1 Introduction 136 6.2 Materials and methods 137 6.3 Results 137 6.4 Discussion 143 Chapter 7 Conclusions and Recommendations 147-150 References 151 Appendices 180 iii List of Tables Tables Title Page Table 2.1 Analytical conditions for light elements determination in water samples on 23 air acetylene flame mood Table 2.2 Analytical conditions for heavy metals determination in water samples by 25 graphite furnace Table 2.3 Analytical conditions for major, heavy and trace elements determination in 32 soil samples Table. 4.1a Description of Physico-chemical parameters of water samples of Attock and 52 Haripur basins, Pakistan Table 4.1b Description of selected elements in surface and groundwater samples Attock 59 and Haripur basins, Pakistan Table 4.2 Drinking water quality guidelines by National and International Agencies. 60 Table 4.3a Pearson’s correlation matrix indicating the association within surface water 66 samples of Attock Basin Table 4.3b Pearson’s correlation matrix indicating the association within groundwater 67 samples of Attock Basin Table 4.4a Pearson’s correlation matrix indicating the association within surface water 70 samples of Haripur Basin Table 4.4b Pearson’s correlation matrix indicating the association within groundwater 71 samples of Haripur Basin Table 4.5a Factor analysis of selected elements in surface water of Attock Basin 74 Table 4.5b Factor analysis of selected elements in groundwater of Attock Basin 75 Table 4.6a Factor analysis of selected elements in surface water of Haripur Basin 77 Table 4.6b Factor analysis of selected elements in groundwater of Haripur Basin 78 Table 4.7 Chronic daily intake (CDI) of heavy metal via the consumption of surface 80 and groundwater in Attock and Haripur basins Table 4.8 Hazard quotient (HQ) of heavy metals via the consumption of surface and 81 groundwater in Attock and Haripur basins Table 5.1 Statistical parameters for major cations distribution in soils of Attock and 94 Haripur basins Table 5.2 Correlation coefficient matrix of selected metals in the soil of Attock Basin 99 Table 5.3 Correlation coefficient