Risk posed by anthropogenically driven toxic pollutants in Abu Qir Bay, East Alexandria, Egypt [Elektronische Ressource] / von Mohammed Abd El-Hamid Khairy Kamal
260 Pages
English
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Risk posed by anthropogenically driven toxic pollutants in Abu Qir Bay, East Alexandria, Egypt [Elektronische Ressource] / von Mohammed Abd El-Hamid Khairy Kamal

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260 Pages
English

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Risk Posed by Anthropogenically Driven Toxic Pollutants in Abu Qir Bay, East Alexandria, Egypt Von der Fakultät für Lebenswissenschaften der Technischen Universität Carolo-Wilhelmina zu Braunschweig zur Erlangung des Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigte D i s s e r t a t i o n Von Mohammed Abd EL-Hamid Khairy Kamal aus Alexandria / Ägypten 1. Referent: Professor Dr. mult. Dr. h. c. Müfit Bahadir 2. Referent: apl. Professor Dr. Ulrich Engelhardt eingereicht am: 16.07.2008 mündliche Prüfung (Disputation) am: 18.08.2008 Druckjahr 2008 Risk Posed by Anthropogenically Driven Toxic Pollutants in Abu Qir Bay, East Alexandria, Egypt A thesis submitted to the Faculty of Life Sciences, Technical University of Carolo-Wilhelmina of Braunschweig, Germany In the partial fulfillment for PhD Degree of Natural Sciences By Mohammed Abd EL-Hamid Khairy Kamal From Alexandria / Egypt 1. Reference: Prof. Dr. mult. Dr. h. c. A. Müfit Bahadir 2. Reference: apl. Professor Dr.

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Published 01 January 2008
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Exrait






Risk Posed by Anthropogenically Driven Toxic Pollutants
in Abu Qir Bay, East Alexandria, Egypt






Von der Fakultät für Lebenswissenschaften

der Technischen Universität Carolo-Wilhelmina

zu Braunschweig

zur Erlangung des Grades eines

Doktors der Naturwissenschaften

(Dr. rer. nat.)

genehmigte

D i s s e r t a t i o n







Von

Mohammed Abd EL-Hamid Khairy Kamal

aus Alexandria / Ägypten






















































1. Referent: Professor Dr. mult. Dr. h. c. Müfit Bahadir
2. Referent: apl. Professor Dr. Ulrich Engelhardt
eingereicht am: 16.07.2008
mündliche Prüfung (Disputation) am: 18.08.2008

Druckjahr 2008






Risk Posed by Anthropogenically Driven Toxic Pollutants
in Abu Qir Bay, East Alexandria, Egypt






A thesis submitted to the

Faculty of Life Sciences, Technical University of

Carolo-Wilhelmina of Braunschweig, Germany

In the partial fulfillment for

PhD Degree of Natural Sciences












By

Mohammed Abd EL-Hamid Khairy Kamal

From Alexandria / Egypt
























































1. Reference: Prof. Dr. mult. Dr. h. c. A. Müfit Bahadir
2. Reference: apl. Professor Dr. Ulrich Engelhardt
Submission date: 16.07.2008
Oral examination: 18.08.2008

2008

Acknowledgments

Praise is to Allah, the lord of all creatures who taught man the whole science and the
names of all things.

This work was carried out during the period from 2006 to 2008 in the Institute of
Ecological Chemistry and Waste Analysis in the Technical University of Braunschweig,
Germany. I am greatly indebted to Prof. Dr. Müfit Bahadir, the head of the institute and
my supervisor for giving me the opportunity to perform this work in Germany under
excellent working atmosphere, his encouragement, patience and interest that he showed in
my work. During the project period, I found him a true academician and I will always
remember him with respect.

My special thanks are due to Dr. Marit Kolb for assisting me during the research
activities, for creative ideas, and especially for the careful reading of my thesis.

No words can express my sincere gratitude to Prof. Dr. Alaa Ramadan Mostafa, Professor of
Organic Geochemistry, Department of Environmental Sciences, Faculty of Science,
Alexandria University, Egypt for his guidance and help during the initial preparation for
this project.

Special thanks to Dr. Anwar EL-Fiky, Assistant Prof. of Hydrogeology for his
participation in the sampling process, his encouragement and his great support.

I would like also to express my deepest thanks to Mrs Christiane Schmidt for her help,
support and encouragement at the beginning of my practical work in Germany. I closely
worked with her throughout the initial stages of this stud and I found in her a decent,
kind and a greatly respective person. I would like to thank her very much for introducing
me to the instruments and her guide during the metal analysis.


I am grateful to all my colleagues in the Institute of Ecological Chemistry and Waste
Analysis for providing a good working environment, working assistance whenever
necessary, and for sharing their scientific knowledge

I am honored to dedicate this thesis to my wife, who sacrified her efforts, time, provided
love and support that made this work possible. Special thanks also for my son Youssouf,
who made the life different since he was born.

Finally, I am greatly thankful for my parents, my sister and my brother for their support
and their encouragement.



























CONTENTS


CONTENTS

1- INTRODUCTION ................................................................................................................... 1
1.1. Environmental problems of coastal areas....................................................................... 1
1.2. Trace metals in the marine environment ........................................................................ 2
1.3. Analysis of trace metals in sediments ............................................................................ 3
1.4. Persistent organic pollutants (POPs) in the marine environment .................................. 4
1.5. Bivalves in marine environmental studies ...................................................................... 7
1.6. Environmental risk assessment ..................................................................................... 9
1.7. Study area ....................................................................................................................... 14
1.8. Previous studies on Abu Qir Bay ................................................................................... 20
1.9. Objectives of the present work ....................................................................................... 22

2- MATERIALS AND METHODS ............................................................................................. 24
2.1. Sampling ......................................................................................................................... 24
2.2. Reagents and chemicals ................................................................................................
2.3. Physicochemical characterization of sediments ............................................................ 27
2.3.1. Sediment grain size analysis .................................................................................
2.3.2. Determination of water content ............................................................................. 28
2.3.3. Determination of total organic carbon (TOC) ........................................................ 29
2.3.4. Determination of calcium carbonate ..................................................................... 29
2.4. Determination of total metals in sediments .................................................................... 29
2.4.1. Sample preparation................................................................................................ 29
2.4.2. ICP-OES analysis...................................................................................................
2.5. Sequential extraction procedures for trace metals in the sediments ............................. 32
2.6. Determination of total metals in mussels ....................................................................... 33
2.6.1. Sample preparation ............................................................................................... 33
2.6.2. ICP-MS analysis.....................................................................................................
2.7. Determination of organic pollutants in sediments .......................................................... 34
2.7.1. Extraction ..............................................................................................................
2.7.2. Cleanup with column chromatography .................................................................. 34
2.7.3. Sulphur removal .................................................................................................... 35
2.8. Determination of organochlorine pesticides and PCBs in mussels ...............................
2.8.1. Extraction ........... 35
2.8.2. Clean up with co................................................................. 36
2.9. Determination of PAHs in mussels ................................................................................. 36
2.9.1. Extraction ........... 36
2.9.2. Clean up with column chromatography 36
2.10. Gas chromatographic analysis ..................................................................................... 36
2.10.1. Standards and calibration ................................................................................... 36
2.10.2. Analysis of chlorinated compounds (GC/ECD) ................................................... 37
2.10.3. Analysis of PAHs (GC/MS) 37
2.11. Quality assurance ......................................................................................................... 38
2.11.1. Determination of the recovery rates .................................................................... 38
2.11.2. Method detection limit (MDL) .............................................................................. 39
2.11.3. Analysis of the certified reference materials ....................................................... 40
3.11.4. Repeatability ........................................................................................................ 40
2.12. Statistical analysis ........................................................................................................ 41

3. RESULTS AND DISCUSSION ............................................................................................. 42
3.1. Physicochemical characterization of Abu Qir Bay sediments......................................... 42
3.2. Metals in sediments of Abu Qir Bay ............................................................................... 43
3.2.1. Spatial distribution ................................................................................................. 44
3.2.2. Chemical partitioning of trace metals in Abu Qir Bay sediments .......................... 48
3.2.3. Normalization of metal concentrations ........................ 53
3.2.4. Comparison of sediment trace metal concentrations with
concentrations worldwide ..................................................................................... 57

I

CONTENTS


3.3. Trace metals in mussel samples of Abu Qir Bay ........................................................... 59
3.3.1. Spatial distribution .................................................................................................
3.3.2. Relation between trace metals in mussel tissues and sediment samples............. 62
3.3.3. Comparison of mussel trace metal concentrations with concentrations worldwide 63
3.4. Polychlorinated biphenyls (PCBs) in the sediment samples of Abu Qir Bay .................. 65
3.4.1. Spatial distribution and possible sources .............................................................. 65
3.5. PCBs in the mussel samples of Abu Qir Bay ................................................................. 70
3.6. Organochlorine pesticides and chlorpyrifos in Abu Qir Bay sediments ......................... 74
3.6.1. DDT and its metabolites (DDTs) ........................................................................... 74
3.6.2. Hexachlorocyclohexane (HCHs) 78
3.6.3. Cyclodiene pesticides ........................................................................................... 80
3.6.4. Methoxychlor, PCBz and HCBz ............................................................................ 83
3.6.5. Chlorpyrifos ........................................................................................................... 83
3.6.6. Influence of the physicochemical properties of the bay sediments on the spatial
distribution of the organochlorine pesticides in Abu Qir Bay ................................. 83
3. 6.7. Comparison between concentrations of chlorinated organic pollutants
in Abu Qir Bay sediments with concentrations worldwide ................................... 84
3.7. Organochlorine pesticides in the mussel samples of Abu Qir Bay 85
3.7.1. Comparison between concentrations of chlorinated organic pollutants
in mussel tissues of Abu Qir Bay with concentrations worldwide ........................ 88
3.8. PAHs in sediments and mussels of Abu Qir Bay ...........................................................
3.8.1. Spatial distribution.................................................................................................. 88
3.8.2. Comparison between PAH patterns in sediments and mussel samples of
Abu Qir Bay ........................................................................................................... 93
3.8.3. Origin of PAHs in Abu Qir Bay .............................................................................. 93
3.8.4. Comparison between concentrations of PAHs in sediments and mussels
of Abu Qir Bay with concentrations worldwide ..................................................... 98

4. RISK ASSESSMENT ............................................................................................................ 100
4.1. Ecological risk assessment (ERA) ................................................................................. 100
4.1.1. Problem formulation ............................................................................................... 100
4.1.2. Exposure characterization...................................................................................... 102
4.1.3. Effect characterization ........................................................................................... 105
4.1.4. Risk characterization ............................................................................................. 113
4.1.5. Areas of special concern based on the conducted SLERA ................................... 119
4.2. Human health risk assessment (HHRA) ........................................................................ 125
4.2.1. Intake assumption .................................................................................................. 125 2. Exposure assessment. 126
4.2.3. Toxicity assessment .............................................................................................. 127
4.2.4. Risk characteriza..... 129
4.2.5.HHRA of other food items in the Egyptian normal diet
compared to the bivalves ........................................................................................ 133

5. Conclusions ......................................................................................................................... 137

6. Summary ............................................................................................................................... 139

Zusammenfassung............................................................................................................... 144

7.References ............................................................................................................................. 150

Appendices

Lebenslauf
II

LIST OF FIGURES


List of Figures

Figure 1: Steps of the ecological risk assessment (ERA) as proposed by USEPA................ 11

Figure 2: Detailed steps of the ERA as proposed by USEPA………………………………….. 12

Figure 3: Map of Abu Qir Bay, Egypt…………………………………………………………...… 15

Figure 4: Contributions of the industrial areas to the flowrate, total suspended solids
(T.S.S.), COD and BOD in Abu Qir Bay (Masoud, 2005)…………………………… 17

Figure 5: Contribution of industrial effluents from the total amount of effluents……………… 18

Figure 6: Mean concentrations of persistent organic pollutants in sediments from different
locations in Egypt (Barakat, 2004)…………………………………………………….. 21

Figure 7: Locations of sampling sites in Abu Qir Bay…………………………………………… 25

Figure 8: Grain size distribution (a) and TOC (%) (b) in surfacial sediments of Abu Qir Bay. 43

Figure 9: Spatial distribution of trace metals in surfacial sediments of Abu Qir Bay………… 44

Figure 10: Percent contribution of each metal fraction from the total concentration in
surfacial sediments of Abu Qir Bay……………………………………………………. 49

Figure 11: Relationships between the reducible fraction of iron (F3) (mg/kg dw) and the
sum of the first three fractions (mg/kg dw) of each trace metal and between the
residual Fe (F5) and the residual fraction of each of the investigated trace metals 54

Figure 12: Ranges and average concentrations of metals (mg/kg dw) in some
representative surfacial sediments worldwide, along the Egyptian Coast and
previously performed on Abu Qir Bay compared to the present work……………... 58

Figure 13: Concentrations (mg/kg dw) of trace metals in mussel samples of Abu Qir Bay
compared to the sediment samples…………………………………………………… 60

Figure 14: Ranges and average concentrations of metals (mg/kg dw) in mussel species
worldwide, along the Egyptian Coast and previously performed on Abu Qir Bay
compared to the present work………………………………………………………….. 64

Figure 15: Spatial distribution of PCBs in surfacial sediments of Abu Qir Bay………………… 66

Figure 16: Chlorine based PCB concentrations (µg/kg dw) in surfacial sediments of Abu Qir
Bay………………………………………………………………………………………… 67

Figure 17: Percent contribution of PCB congeners in selected surfacial sediments of Abu
Qir Bay from the Abu Qir Drain region (stations 1, 2, 20 and 21), between the
Fertilizer Company and the Electric Power Plant (stations 18 and 19) and the
Maadeya region (stations 4, 8, 13 and 14)……………………………………………. 68

Figure 18: Percent contribution of PCB congeners in mussel tissues based on the number
of Cl atoms. Stations 4 to 19 represent Mactra corallina and 25 to 27 represent
Tapes decussata………………………………………………………………………… 72

Figure 19: Distribution of PCB congeners in sediment samples and mussel tissues of Abu
Qir Bay……………………………………………………………………………………. 73

III

LIST OF FIGURES


Figure 20: Spatial distribution of organochlorine pesticides in surfacial sediments of Abu Qir
Bay………………………………………………………………………………………… 75

Figure 21: Distribution of DDTs and its metabolites in surfacial sediments of Abu Qir Bay….. 76
Figure 22: Percent contribution of DDT and its metabolites (DDD and DDE) in surfacial
sediments of Abu Qir Bay………………………………………………………………. 78
Figure 23: Isomeric concentrations of HCHs in surfacial sediments of Abu Qir Bay…………. 79
Figure 24: Percent contribution of HCH isomers in surfacial sediments of Abu Qir Bay……... 80
Figure 25: Concentrations of cyclodiene pesticides (µg/kg dw) in surfacial sediments of Abu
Qir Bay……………………………………………………………………………………. 81
Figure 26: Ranges and average concentrations of PCBs and DDTs (µg/kg lipid weight) in
mussel species worldwide, along the Egyptian Coast and previously performed
on Abu Qir Bay compared to the present work………………………………………. 85
Figure 27: DDT metabolites in mussel tissues of Abu Qir Bay. Stations 4 to 19 represent
Mactra corallina and 25 to 27 represent Tapes decussata…………………………. 86
Figure 28: Distribution of HCH isomers in mussel tissues of Abu Qir Bay. Stations 4 to 19
represent Mactra corallina and 25 to 27 represent Tapes decussata……………… 87
Figure 29: Ranges and average concentrations of PCBs and DDTs (µg/kg lipid weight) in
mussel species worldwide, along the Egyptian Coast and previously performed
on Abu Qir Bay compared to the present work………………………………………. 88
Figure 30: Spatial distribution of PAHs (µg/kg dw) in surfacial sediments of Abu Qir Bay…… 89
Figure 31: Percent contribution of the molecular mass profile of PAHs in surfacial sediments
(a) and mussel samples (b) of Abu Qir Bay…………………………………………... 90
Figure 32: Comparison of PAH patterns of sediment and mussel samples of Abu Qir Bay…. 94
Figure 33: Phn/Ant versus Fla/Pyr plots for PAHs in sediments (a) and mussels (b) of
Abu Qir Bay………………………………………………………………………………. 96
Figure 34: Molecular ratios applied for PAHs in sediments (a) and mussel samples (b) of
Abu Qir Bay………………………………………………………………………………. 97
Figure 35: Ranges and average concentrations of PAHs (µg/kg) in surfacial sediments (a)
and mussel species (b and c) worldwide and along the Egyptian Coast
compared to the present work………………………………………………………….. 99
Figure 36: Conceptual site model for the SLRA in Abu Qir Bay………………………………… 103
Figure 37: SLERA approach applied in Abu Qir Bay……………………………………………... 114
Figure 38: TEC HQ (a) and PEC HQ (b) for trace metals in Abu Qir Bay sediments………… 115
Figure 39: TEC HQ and PEC HQ for chlorinated organic compounds (a) and PAHs (b)
in sediments of Abu Qir Bay……………………………………………………………. 116
Figure 40: Geographical distribution of HQ in Abu Qir Bay sediments…………………………. 120
Figure 41: Tissue concentrations of trace metals (a) and PAHs (b) in Mactra corallina
and Tapes decussata investigated in the present work compared to toxicity
concentrations reported in literature…………………………………………………… 124
IV