ميحرلانمحرلاهللا مسب Sudan Academy of Sciences (SAS) Atomic Energy Council Assessment of Some Heavy Metals in Fruit from Local Market in Khartoum State A thesis submitted in partial fulfillment of requirements for the degree of M.Sc. in Nuclear Sciences & Technology By Maha Bashir Omer (B.Sc. Hons chemistry, Al-Neelain University) Supervisor: Dr. Amel Yousif Ahmed January 2015 Sudan Academy of Sciences (SAS) Atomic Energy Council Assessment of Some Heavy Metals in Fruit from Local Market in Khartoum State By: Maha Bashir Omer Examination committee Title Name Signature Supervisor Dr. Amel Yousif Ahmed External Prof. Mustafa M.O. Ahmed Examiner January 2015 DEDICATION I dedicate this work to: To my family i ACKNOWLEDGMENT This work would not have possible without the guidance and the help of several individual who in one way or another contributed and extend their valuable assistance in the preparation and completion of this study. First I express my thanks and sincere gratitude to my supervisor Dr. Amel Yousif Ahmed for suggesting the problem and her valuable advice. I thank to Miss Khalda Awaad and Mr Osama from radio isotopes lab for all their help and patience.and to all workers in environmental monitoring of radioactivity lab. And also full thank to Sudan atomic energy commission and for the former director Prof Mohammed Ehmed Hassan Eltayeb for this opportunity. I like to thank my husband and son daughter and sisters Safa for their, support and encouragement in supporting this project. Finally greater thank to my best friends Mohammed Hassan and all who helped me and stood with me to perform this work in this form. ii ABSTRACT Fruits play important role in providing the individuals daily dietary needs from vitamins iron, calcium, potassium and some metals that need in the daily food as dietary supplementation or as an important elements that form some hormones or enzymes in small concentrations , if exists in high concentrations become toxic with bad effects. This study aims to detect some of metals and find this elements their concentrations in some fruits that is most consumed in Sudan which are: bananas, oranges, tomatos and watermelons. These fruits were randomly collected from local markets in Khartoum state from the three localities: Khartoum, Bahri and Omdurman. Another sample was collected from the original farm to represent the control samples. That’s to compare the concentration of metals in it with the random one using xrf technique. Euch sample was dried and pressured into pulled to be analyze it. The following metals were detecting: Br, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, Rb, Sr and Zn in ppm K, Ca and Fe measured in g/kg. It was found that the mean concentration of these metals in banana: 52.66, 28.01, 50.31, 15.79, 0.57, 31.98, 60.92, 10.07, 1.42, 18.41, 5.37 and 19.22 respectively. And the mean concentration of them in orange: 6.80, 9.83, 19.00, 52.88, 0.35, 26.54, 13.05, 41.53, 1.74, 49.80, 14.85 and 15.41 respectively. The mean concentration of them in tomato: 39.30, 5.45, 50.52, 20.03, 0.88, 62.45, 82.13, 9.44, 1.79, 59.78, 26.38 and 41.31 respectively. The mean concentration of metals in watermelon: 33.00, 6.96, 26.08, 14.30, 1.32, 43.93, 52.67, 6.01, 1.69, 38.51, 43.90 and 25.45 respectively It is noted that these concentrations were far higher than the concentrations in other countries underwent the same study. The statistics showed in some fruits that the significant ratio between the case and the control was p < 0.05 i.e. the significance is different and may be caused by pollution. iii مستخلص تلعب الفواكه ا دور هاما في تزويد الفرد باحتياجاته اليوميه من الفيتمينات والحديد والكالسيوم والبوتاسيوم وبعض المعادن التي يحتاج اليها في غذاءه اليومي كمكمل غذائي او كعنصر مهم يدخل في تركيب بعض الهرمونات أو اﻹنزيمات بتراكيز صغيرة . إذا زادت هذة العناصر عن حدها المطلوب أصبحت عبارة عن سميات يكون لها تاثير سلبي . تهتم هذة الدراسه بتحديد بعض المعادن الثقيله وتراكيزها في بعض الفواكهة اﻷكثر استهﻻكا في السودان وهي الموز ,البرتقال ,البطيخ والطماطم, تم جمع هذة الفواكهة عشوائيا من ثﻻثة أماكن مختلفة بوﻻية الخرطوم وهي الخرطوم , أمدرمان وبحري وكان الجمع من اﻷسواق المحليه , وجمعت عينات موازيه لها كعينات ضابطه من الحقل من مناطق اﻹنتاج اﻻصليه لكل فاكهة لمقارنة مستوي تركيز العناصر فيها مستخدمين تغنية فلورة اﻻشعة السينيه . جففت العينات وضغطت ثم رصدت العناصر اﻻتيه البروم, الكالسيوم, الكروم, النحاس, الحديد, البوتاسيوم, المنجنيز, النيكل, الرصاص ,الربيديوم, اﻻسترانشيوم, و الزنك , وكانت تراكيز متوسطات المعادن بجزء لكل مليون عدا البوتاسيوم والكالسيوم والحديد جم/كجم . وكانت تراكيز متوسطات المعادن للموز كاﻷتي: 19.22 , 5.37, 18.41 ,1.42 , 10.07 , 66.92 , 31.98 , 0.56 , 15.79 , 50.31, 2.01, 52.66 علي التوالي. ونتائج تراكيز متوسطات المعادن للبرتقال كاﻷتي : , 83.. , 0..8 , 80.89 , 09.68 , 6.98 , 40.88 ,88... , 03.66 , 3..9 , 0..6 8..08 , 08.80 علي التوالي. وكانت تراكيز متوسطات المعادن للطماطم كاﻷتي: , 83... , 0..3 , 3.88 , .4.09 , 04.88 , 6... , 46.69 , 86.84 , 8.88 , 93.96 .40.9 , 80.90 علي التوالي. وكانت تراكيز متوسطات المعادن في البطيخ كاﻷتي: , 9..80 , 0.03 , 0.60 , 84.0. , 89.39 , 0.94 , 08.96 , 40.6. , 0.30 , 99.66 89.3 , 48.88 علي التوالي. وهي اكبر بكثيرمن متوسطات مماثله لها ا’جريت في بعض الدول . ودلت نتائج التحليل اﻻحصائي علي ان مستوي المعنويه في أغلب الفواكهة أقل من 6.68 وهذا يدل علي فروق معنوية كبيره في بعض الفواكهة مما يدل ايضا علي وجود ملوثات. iv TABLE OF CONTENTS Title Page Dedication i ACKNOWLEDGEMENT ii Abstract (English) iii Abstract(Arabic) iv Table of Contents v List of Table vii List of Figures viii Chapter One Introduction 1.1 Introduction 1 1.2 Heavy metal 2 1.2.1 Definition of heavy metals in plant science 2 1.2.2 Toxic effect 3 1.2.2.1 lead 3 1.2.2.2 Zink 4 1.2.2.3 Nickel 5 1.2.2.4 Iron 5 1.2.2.5 Copper 6 1.2.2.5 Chromium 6 1.2.2 Bromide 7 1.2.2.7 Strontium 7 1.2.2.8 Rubidium 7 1.3 Heavy metals in plant 8 1.4 X-Ray Fluorescence (XRF) 8 1.4.1 Introduction 8 1.4.2 Underlying physics 8 1.4.3 X-ray production 10 v 1.4.4 Characteristic radiation 11 1.4.5 Chemical analysis 12 1.4.6 Procedure of x-ray fluorescence analysis 13 1.4.7 Basic principles 13 1.4.8 Advantage 14 1.4.9 Applications 14 Chapter Two Literature Review 2.1 Metal in fruit 15 2.2 XRF 17 2.2.1 History of XRF 17 2.2.2 literature review of XRF 18 2.3 T-test 18 2.3.1 The t-test and basic inference principles 18 2.3.2 Tow side t -test 19 2.4 Problem Statement 20 2.5 Objective of studies 20 2.6 Outline of the study 20 Chapter Three Materials and Method 1.3 Sample collection 21 3.2 Sample preparation 21 3.3 Sample analysis 24 Chapter four Result and Discussion 4.1 Quality control of the obtained data 26 4.2 Summary of statistics 28 4.3 Comparison between sample and control sample 35 Conclusion 43 Recommendation 43 Reference 44 vi List of Table Title Page Table1.1 Classification of some metals and metalloids according covalent 2 index Table 4.1 Concentration of heavy metal of analytical hay powder ppm 26 compare with certificate value gm/kg Table 4.2: Summary of the statistics for the metals concentration ppm 28 except K,Ca and Fe g/ kg in banana samples using XRF Table 4.3: Summary of the statistics for the metals concentration ppm 29 except K,Ca and Fe control samples Banana using XRF Table 4.4: Summary of the statistics for the metals concentration PPM 30 except K,Ca and Fe g/kg in orange samples using XRF Table 4.5: Summary of the statistics for the trace elements concentration 30 ppm for the bulk control samples orange using XRF Table 4.6: Summary of the statistics for the heavy metals concentration 31 ppm except Fe ,K,Cag/kg for samples tomato using XRF Table 4.7: Summary of the statistics for the trace elements concentration 32 ppm for the bulk control samples tomato using XRF Table 4.8: Summary of the statistics for the trace elements concentration 33 ppm for the bulk samples watermelon using XRF Table 4.9: Summary of the statistics for the trace elements concentration 34 ppm for the bulk control samples Watermelon using XRF Table 4.10 t-test result for banana 35 Table 4.11 t-test result for orange 36 Table 4.12 t-test result for watermelon 36 Table 4.13 t-test result for Tomato 37 vii List of Figures Title Page Fig. 1.1: Physics of x-ray fluorescence in a schematic representation 9 Fig. 1.2: X-ray tube 11 Fig. 1.3 The main transitions 12 Fig. 1. 4: Schematic spectrometer arrangement of EDX 13 Fig. 3.1 Silece of banana 21 Fig. 3.2 Oven 22 Fig. 3.3 Sensitive acale 23 Fig. 3.4 Pressing machine 23 Fig. 3.5 Pellet diameter 2.5cm 24 Fig. 3.6 XRf machine 25 Fig. 4.1 Show error percentage of detect 27 Fig.