Use of Nuclear Spectroscopic Techniques for Assessment of Polluting Elements in Environmental Samples Ph. D. Thesis Submitted for the degree of the Doctor of Philosophy of Physics By Hoda Ismail El-Reefy (M.Sc. Physics, 2004, Tanta University) Hot Laboratories Center, Atomic Energy Authority Supervisors Prof. Dr. T. Elnimr Prof. Dr. T. Sharshar Prof. of Biophysics, Prof. of Experimental Nuclear Physics, Physics Department, Physics Department, Faculty of Science, Faculty of Science, Tanta University, Kafrelsheikh University, Tanta, Egypt. Kafr El-Sheikh, Egypt. Prof. Dr. N.A. Belacy Prof. Dr. A.M. Hassan Prof. of Physical Chemistry, Prof. of Experimental Nuclear Physics, Hot Laboratories Center, Nuclear Research Center, Atomic Energy Authority, Egypt. Atomic Energy Authority, Egypt. To Physics Department, Faculty of Science, Tanta University 2011 Supervisors Prof. Dr. T. Elnimr Prof. of Biophysics, Physics Department, Faculty of Science, Tanta University, Egypt. Prof. Dr. T. Sharshar Prof. of Nuclear Physics, Physics Department, Faculty of science, Kafr El-Sheikh University, Kafr El-Sheikh, Egypt. Prof. Dr. N.A. Belacy Prof. of Physical Chemistry, Hot Laboratories Center, Atomic Energy Authority, Egypt. Prof. Dr. A.M. Hassan Prof. of Experimental Nuclear Physics, Nuclear Research Center, Atomic Energy Authority, Egypt. Head of Physics Department Prof. Dr. H. M. Badran CURRICULIUM VITAE Name : Hoda Ismail El-Reefy Nationality : Egyptian Date of Birth : Aug. 6, 1959 Place of Birth : Alexandria, Egypt Email address : [email protected] Religion : Moslem Qualifications • M.Sc. of Physics – Faculty of science, Tanta University– Egypt. (2004) • B.Sc. of Physics – College of Girls, Ain Shams University– Egypt. (1980) Head of Physic Department Prof. Dr. H. M. Badran ACKNOWLEDGMENT I am grateful to all the honorable supervisors and collaborative, the works of whom have made the completion of this thesis possible. My special thanks are due to Prof. Dr. T. Elnimr Physics Department, Faculty of Science, Tanta University, Prof. Dr. T. Sharshar, Physics Department, Faculty of Science, Kafr El-Shaikh University, Prof. Dr. N.A. Belacy, and Dr. M.A. Hilal Hot Laboratories Center, AEA, and Late Prof. Dr. A.M. Hassan Nuclear Research Center, AEA for their keen interest, logical observations, constructive suggestions, and kind cooperation throughout this study. The appreciable voluntary efforts, made by Prof. Dr. H.M. Badran head of Physics Department, Faculty of Science, Tanta University, in helping and bringing out this thesis in its present form, are thankfully acknowledged. It is my pleasure to thank Prof. Dr. R. Zaghloul, Professor of Nuclear Physics, Hot Laboratories Center, AEA and Prof. Dr. S.A. El-Reefy for their help and guidance all the way through my career. Thanks are also due to my colleagues in Radioanalysis Researsh Lab, Faculty of Science, Tanta University for their valuable support and encouragement, notably Dr. Khalid Ramadan. I am greatly thankful to my Husband Dr Atef Eldesouky for his endurance during the time I was awfully busy in not only in producing this work but also throughout my research career. Thanks are also due to my daughter Dr. Eiman and my sons Eng. Ahmed, and Eng. Amgad, who gave me the moral support and had to bear the loss of my full company during their pleasurable young days. IV Abstract The concentrations of elements and radioisotopes in sediment, soil, water and wild plant samples collected from Burullus Lake, Egypt, has been studied in order to understand current contamination due to agricultural and industrial wastewaters. A multiple approaches were applied to assess properly sediment contamination in the Burullus Lake. The distributions of the Al, Fe and Mn in the lake’s sediments are relatively homogenous with the exception of three locations with significantly high levels of Al and Fe in close approximation in the southeastern part. Sediments collected from the lake can be categorized as unpolluted with the exception of three locations which were very low polluted with Sr based on the geo-accumulation indices. High enrichment factors were obtained for Mn, Co, Cr, Cu and Zn. The MPIs indicate that one of the drain may have a major role in mobilizing major and trace metals in the lake environment while cluster analysis indicates possible pollution from only three of the drainage channels. Comparisons with consensus-based sediment quality guidelines revealed that 100%, ~69%, ~92% and ~15% of the samples exceeded the threshold effect concentration for Cr, Cu, Ni and Zn, respectively, with over 15% for Cr and Ni of the sample concentrations falling above the probable effect concentration. On the other hand, no samples exceed both levels for Pb. The concentration of 40K is uniform and that of 137Cs is generally higher in eastern part of the lake. The result indicate that 226Ra is less soluble in the lake environment than 232Th. Elemental concentrations in water have uniform distributions and the Fe, Mn, Co, Cr, Cu and Ni are more likely to exist in soluble phase in the lake environment. 40K concentrations are higher in Sinjar region and sediment-water distribution coefficients of 40K decreases with increasing water salinity. Concentrations of major and trace elements in soil are higher in Sinjar Island than Al-Koum Al-Akhadr Island. Similarly, Sinjar Island have higher V activities of NORM but lower activity of 137Cs than those in Al-Koum Al- Akhadr Island. There is no high radiation exposure to the humans in the study area from soil. No dependence of the concentrations of radioisotopes in wild plants on the specious of the plants included except for 40K isotope was found. VI TABLE OF CONTENTS Acknowledgment IV Abstract V Table of Contents VII List of Tables XI List of Figures XIV Abbreviations XVI 1. Introduction 1.1 Environmental Pollution 1 1.2 Radionuclide Pollutants 2 1.2.1 Natural and artificial radioactivity 4 1.2.2 Equilibrium in radioactive decay 7 1.3 Heavy Metal Pollutants 9 1.4 Potential Health Effects of Radiation and Heavy Metals 10 1.5 Quantitative Analysis of Radioactive and Heavy Metal Pollutants 17 1.5.1 High purity germanium (HPGe) gamma-ray spectroscopy 18 1.5.2 Inductively coupled plasma optical emission spectrometry 20 1.5.3 Neutron Activation Analysis 21 1.5.4 K0-standardization method 24 1.6 Review of Relevant Studies 24 1.6.1 Related studies of Burullus Lake 24 1.6.2 General studies in other locations in Egypt 26 1.6.3 Related studies from different countries 29 2. Study Area 2.1 Lake Location 33 2.2 Economical Benefits of the Lake 34 2.3 Lake Depth 35 VII 2.4 Water Resources 36 2.5 Water Balance 37 2.6 Habitat types 38 2.6.1 Salt marshes 38 2.6.2 Sand formations 38 2.6.3 Lake cuts 39 2.6.4 Drains 39 2.6.5 Lake proper 40 2.6.6 Islets and Islands 40 2.7 Aim of the Work 41 3. Experimental Methods 3.1 Quick Overview of Sampling and Sample Preparation 43 3.2 Sampling 45 3.2.1 Sediment samples 45 3.2.2 Water samples 46 3.2.3 Soil samples 46 3.2.4 Vegetation samples 47 3.3 Sample Preparation 50 3.3.1 Samples preparation for passive radiation measurements 51 3.3.2 Sample preparation for elements measurements 52 3.4 Measurements of Sample Characteristics 54 3.4.1 pH value 56 3.4.2 Total dissolved solids content 58 3.4.3 Total organic matter content 58 3.4.4 Grain size fractions 59 3.4.5 Calcium carbonate 59 3.5 Measurements of γ-Ray Emitting Radionuclide 60 VIII 3.5.1 Energy and efficiency calibrations 60 3.5.2. Statistical considerations 64 3.6 Dosimetry Assessments 66 3.7 NAA Measurements 68 3.7.1 Sample irradiation and activity measurements 68 3.7.2 Efficiency calibration for NAA measurements 69 3.7.3 Calculation of element concentration 70 3.8 ICP Measurements 72 4. Results and Discussion 4.1 Characteristic of the Samples 73 4.1.1 Sediments 73 4.1.2 Water 74 4.1.3 Soil 75 4.1.4 Wild Plants 79 4.2 Radioactivity Concentrations 82 4.2.1 Sediments 82 4.2.2 Water 91 4.2.3 Soil 94 4.2.3 (a) Dosimetry assessment 101 4.2.4 Wild plants 102 4.2.4 (a) Soil-to-plant transfer factors 103 4.3 Elemental Analysis 106 4.3.1 Comparative study of ICP and NAA measurements 106 4.3.2 Sediment samples 107 4.3.2 (a) Major elements (Al, Fe and Mn) 108 4.3.2 (b) Trace elements 113 4.3.2 (c) Comparison with similar local studies 118 IX 4.3.2 (d) Assessment of sediment pollution and toxicity 118 4.3.2 (e) Statistical analysis 136 4.3.2 (f) Cluster analysis 145 4.3.3 The absolute contents in water samples 148 4.3.4 The absolute contents in soil samples 158 4.3.5 The absolute contents in wild plant samples 159 APPENDICES 163 REFRENCES 166 SUMMARY i أ ARABIC SUMMARY X List of Tables 1 List of Tables № Tables Page 1-1 Basic characteristics of the four radioactive series 5 3-1 Wild plant included in the present study and their sampling 49 locations. The wild plant scientific, family and common names are also given together with their abundance. 3-2 The energies of γ-ray lines used for determination of element 72 concentrations. 4-1 Characteristics of sediment samples collected from the study 76 area. 4-2 Statistical data of some characteristics of sediment samples. 77 4-3 Characteristics of water samples. 79 4-4 Descriptive statistics of water characteristics. 79 4-5 The concentrations of NORM and 137Cs in Bq kg–1 DW (dry 83 weight) for the sediment samples collected from Burullus Lake.