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Organochlorine Residues in the Riverine Ecosystem of Pakistan

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Organochlorine Residues in the Riverine Ecosystem of Pakistan Organochlorine Residues in the Riverine Ecosystem of Pakistan by Syed-Ali-Musstjab-Akber-Shah, Eqani A thesis submitted in partial fulfillment of the requirement for the degree of Doctor of Philosophy in Environment Biology Department of Plant Sciences Quaid-i-Azam University Islamabad, Pakistan 2012 07-08-2012Page I Page I Dedicated To MMyy SSwweeeett MMootthheerr aanndd CCuuttee SSoonn JJaallaall ((LLaattee)) Page II DECLERATION The material contained in this thesis is my original work, except where acknowledge. No part of this thesis has been previously presented elsewhere for any other degree. Syed-Ali-Musstjab-Akber-Shah, Eqani Page III Acknowledgments. All worships and praises are only due to the Almighty Allah, The compassionate, The merciful, Who gave us health, thoughts, strength and potential to achieve the recommended tasks. I owe my deep respect to Hazrat Muhammad (PBUH) and Panjtan Pak (A.S.), who are forever the torch of guidance and light of knowledge for mankind. I would like to express my deepest gratitude and sincere thanks to Prof Dr. Asghari Bano (Dean/Chairperson) for her keen interest, providing her precious time and valuable insight for this practicum. Special thanks are due to Dr. Riffat Naseem Malik (Research Supervisor) and Prof. Dr. Gan Zhang(Foreign Supervisor), State Key Laboratory of Organic Geochemistry, Guangzhou Institute of organic Geochemistry, Chinese Academy of Sciences for providing necessary lab facilities regarding the organochlorine residues analysis of water, sediment, and fish samples. Many thanks to Dr. Paromitta, Dr Linthoi, Dr. Jun Li, Dr. Liu Xiang, Mrs. Li Li, Mrs. Jenny, Mr. Chang, and Mr. Lewis for their support and guidance during laboratory work at CAS, China. I feel most pleasure in expressing my heartiest gratitude for Dr. Ashiq Muhammad (Co- supervisor), Ecotoxicology Research Laboratory, IPEP, NARC Islamabad for his reliable suggestions, affectionate and encouragement during my time at the NARC. I also wish to thank the most respected Dr. Syed Zahoor Hussain, Richard Garstang (NPM/ Chief Organizer, PWP), Dr. Mumtaz H. Taqi, Dr. Rafiq (Director Fisheries), Dr.Azhar Rashid, Dr. Ali RazaGurmani, Dr. Abdul Qadir, Dr. Masood Arshad, Mr. Ahmad Khan (PWP), Mr. Usman (GIS expert), Mr. Naveed Qaiser, Dr. Rashid, Ghulam Abbass Haideri, Saadat Hassan Kunjal, Rabia Riasat and Dr. Maria Ali for their guidance and support during this project. Special thanks to Jabir Hussain Syed, Mr. Adeel, Mr. Usman Ali, Raja Rizwan Ullaha, Hina Qayyum, M. Nadeem, Samiya Farooq, Mr. Z.A. Malik, Sadia Rasheed, Sidra Waheed, Azmat Zehra, Ambreen Syed, Sidra Rauf Minhas, Naila Zeb, Imran Khosa, Aqeel Kamran,Tabbsum Abbas (Gagoo), Iltaf Chadhar (Tafa), Iltaf Hussain (Shadda) and Usman Khan for their support during field and laboratory work. Deep gratitude to Mr. Azhar Khan (S.D.O. Irrigation Department) for providing necessarily inputs and residence during Page IV exhaustive field sampling. I am also thankful to Sadqat Hussain (Driver, PWP), Javed Iqbal (Driver PWP), Muhammad Sadiq (Fisherman), Banarus Chacha (Fisherman) and Liaqat Abbasi (Lab Attendant), who really helped me in this project, even more than my expectations. I ought to submit my sincere feelings to my family members Abu Jan, Shajar Batool (wife), Syed Ali Mushaf (brother), Shabia (sister), Syed Awon Abbas, Baji Kaosar and his family, Sweet Novee, Babboo (Kanita), Naqi Shah, Uncle Syed Mohsin Shah, Uncle Gazanfar, Uncle Hussnain, Uncle Qaiser, Uncle Jafri, Anti Ishtiaq, and Anti Asia for their moral support throughout the course of my research work. I have no word of appreciation for my sweet cousin Laila Jafri for her moral/technical support throughout my PhD. studies. I ever remember the sweet memories of my respected cousin Syed Ahmad Raza Naqvi (Late), who really support, guide, and encourage me to achieve this mile stone. EQANI SAMAS Page V Table of Contents Chapter # Title Page # Acknowledgments IV List of Figures X List of Tables XII List of Appendices XIV List of Abbreviations XV Abstract XVIII 1 Introduction and Review of Literature 1.1 General Introduction 1 1.2. Occurrence and distribution of organochlorine contaminants in water, sediment/soil and 3 biota from Pakistan: a review 1.2.1. Organochlorines contamination in the surface and ground waters from Pakistan 3 1.2.2. Organochlorines contamination in the sediments/ soils from Pakistan 5 1.2.3. Organochlorine residues in the biota from Pakistan 8 1.3. Problem Statement 14 1.4. Objectives of the Study 15 1.5. Structure of Thesis 15 2 Materials and Methods 17 2.1. Study area 17 2.2. Field strategies 18 2.3. Sample collection 23 2.3.1. Water 23 2.3.2 Sediment 23 2.3.3. Fish 23 2.4. Experimental section 24 2.4.1. Water 24 2.4.1(a). Physicochemical parameters 24 2.4.1(b). Extraction and clean-up 25 2.4.2. Sediment 25 2.4.2(a). Physicochemical parameters 25 Page VI Chapter # Title Page # 2.4.2(b). Extraction and purification 26 2.4.3. Fish 26 2.4.3(a). Identification, sample preparation, and measurement of biological parameters 26 2.4.3(b). Extraction, lipid (%) determination and purification 27 2.4.3(c). Isotopic analysis 28 2.5. Chromatographic analysis 30 2.6. Quality assurance and Quality control (QA/QC) 30 3 Occurrence, Fingerprinting, and Risk Characterization of OCPs and PCBs in the 32 Surface Water of the River Chenab, Pakistan. 3.1. Material and Methods 32 3.1.1. Statistical analysis 32 3.2. Results 33 3.2.1. Physicochemical parameters of the surface water 34 3.2.2. Remarks on the level of distribution of OCPs and PCBs 35 3.2.3. Classification of the sampling sites 46 3.2.4. Source Identification using Factor Analysis (FA/PCA) 47 3.3. Discussion 53 3.3.1. Organochlorine distributional patterns in a global perspective 53 3.3.1(a). HCHs 53 3.3.1(b). DDTs and their sources 54 3.3.1(c). Chlordanes 55 3.3.1(d). Other OCPs 55 3.3.2. Difference in PCB congener profiles 56 3.3.3. Spatio-Temporal variation of OCPs and PCBs 57 3.4. Toxicity imposed due to OCPs and PCBs 60 3.5. Conclusion 62 4 Occurrence, Distribution, Possible Sources and Ecotoxicological Concern of OCPs 63 and PCBs in the Surface Sediments Collected From River Chenab, Pakistan. 4.1. Materials and Methods 63 4.1.2. Statistical analysis 63 4.2. Results 64 Page VII Chapter # Title Page # 4.2.1. Characterization of sediments 64 4.2.2. Concentration profile of OCPs and PCBs in sediments 65 4.2.3. Classification of sampling sites 77 4.2.4. Source identification using Factor Analysis (FA/PCA) 78 4.3. Discussion 86 4.3.1. Characterization of OCP concentrations in sediment 86 4.3.1(a). HCHs 86 4.3.1(b). DDTs and its extent of pollution 87 4.3.1(c). Chlordanes 89 4.3.1(d). Other OCPs 89 4.3.2. PCB behavior and approximation of their possible sources 90 4.3.3. Spatial and temporal distribution of OCPs and PCBs in the sediment 92 4.4. Ecotoxicological concern for OCPs and PCBs in sediment of River Chenab 95 4.5. Conclusions 98 5 Organochlorine Pesticides (OCPs) and Polychlorinated biphenyles (PCBs) in Fresh 99 Water Fish Collected from the River Chenab, Pakistan: Levels, Accumulation Features, and Risk Assessment 5.1. Materials and Methods 99 5.1.1. Statistical Analysis 99 5.1.2. Bioconcentration factors (BCF) and Biota-sediment accumulation factor (BSAF) 99 5.1.3. Toxic equivalency calculations 100 5.1.4. Risk characterization 100 5.3. Results 101 5.3.1. The biological characteristics and tropic levels of collected fish species 101 5.3.2 OCP loads and their accumulation patterns 104 5.3.3 PCB concentrations and profile distribution 106 5.3.4. Dioxin-like PCBs contribution 107 5.3.5. Seasonal variation of OCPs and PCBs 118 5.3.6. Spatial variation of OCPs and PCBs 120 5.4. Discussion 123 Page VIII Chapter # Title Page # 5.4.1. OCP signatures in fish: general observation 123 5.4.1(a). HCHs 123 5.4.1(b). DDTs 124 5.4.1(c). Chlordanes 125 5.4.1(d). Other OCPs 126 5.4.2. Congener-specific profile for PCB and their environmental significance 127 5.4.3. Toxicity imposed due to dioxin-like PCBs 128 5.4.4. Bioaccumulation of OCPs and PCBs in the fish from River Chenab 129 5.4.5 Partitioning behavior of OCPs and PCBs 133 5.5. Risk assessment of OCPs and PCBs in the fish collected from River Chenab 135 5.5.1. Maximum Admissible Concentrations (MACs) 136 5.5.2. Minimal Risk Level (MRL) 136 5.5.3. Potential risk 137 5.6. Conclusion 143 6. General Discussion, Recommendations and Future Thrusts, and Broucher for Policy 144 Makers 6.1. General summary 144 6.1.1. Occurrence, distribution, and finger printing of OCP and PCB in the surface water and 145 sediment from River Chenab, Pakistan 6.1.1(a). Site-specific distributional patterns 146 6.1.1(b). Seasonal variation 148 6.1.2. Bioaccumulation features of organochlorine in the collected fish from River Chenab 149 6.1.3. Ecotoxicological concern of OCP and PCB in different environmental compartments 151 6.2. Concludary remarks 152 6.3. 6. Recommendations and future thrusts 154 6.3.1. For academic and research institutions 154 6.3.2. For national and regional environmental authorities 155 6.3.3. For water and sediment quality 155 References 157 Appendices 181 Research Publication 229 Page IX List of Figures Fig# Title Page # Fig.1.1. Showing the study locations discussed in the Chapter 1 along with the contribution of OCPs.
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