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Benzene Exposure from Automobiles Fuelled// with Petrol BENZENE EXPOSURE FROM AUTOMOBILES FUELLED// WITH PETROL A thesis submitted in accordance with the conditions governing candidates for the degree of DOCTOR OF PHILOSOPHY To The University of Newcastle-upon- Tyne By Nabeel Mansour Al-Khulaifi B.Sc. (Kuwait University) M.Sc. Environmental Health (Boston University !Massachusetts) December 2002 Department of Environmental and Occupational Medicine The Medical School University of Newcastle Newcastle upon Tyne, NE2 4HH United Kingdom NEWCASTLE UNIVERSITY LIBRARY , ----------------------------. 201296730 ---------------------------- In the name of Allah, Most Gracious, Most Merciful. Praise be to Allah The Cherisher and Sustainer of the Wodds. (Quran, 1985) CERTIFICATE I hereby certify that the work embodied in this thesis is the result of my own investigations, except where reference has been made to published literature. Candidate: Directors of Studies: Signed: Professor P .G. Blain DECLARATION I hereby declare that this work has not been accepted in any substance for any degree, and is not concurrently submitted in candidature for any degree. Candidate: To My Father "Mansour AI-Khulaifi" My Mother "Nora AI-Obaid" My Wife "Raya AI-Rukhiess" My Son "Abdul-Rahman" My Daughters "Monira & Nora" 3 ACKNOWLEDGEMENT /" First of all, I would like to express my gratitude to the Kuwait Public Authority of Applied Education and Training for the opportunity they gave me to do this research with their fmancial and ethical support and their understanding of the research difficulties that I've faced during the time course of the study. The research work was a new approach and consists of a spectrum of technical challenges. I have been privileged to work in the Environmental and Occupational Medicine Department in the University of Newcastle. I am grateful for the supervision of Professor Peter Blain and Dr. Ovnair Sepai.. Dr. Faith Williams and Dr . Elaine Mutch have provided encouragement and support for this work. Also, I'm very grateful to Mr. David Sutherland and Mr. David Henderson for their substantial technical help. I wish to acknowledge with thanks the generous contribution from all friends and colleagues to the study. Mr. David Foster, Mr. Gorden Smith and Mr. Andrew Hall (members of Newcastle Occupational Health in Newcastle General Hospital) were very helpful in the fieldwork. 4 CONTENT Aim ................................................................................................... ~;•••••••.••••.••••••••••••••• 8 Objectives •.••••••••••••••••••..•••••.•••••.••.•.••••••••••••.••••.••.••••.••••••••••••••••.•.•••••...•••••••••••••••••••••••••• 8 Abstract •.......•...........•....••.•.......•....•..............•.......•....•.••.•...•.................••.....•.••..•...........• 9 List of Tables· .•••••••••••••••••.•••.••.•.••••••.•.•••••.•.•••.•••••••.••••••••••••••.•.••.•••••••••.•....•.••••••••..•••.••• 10 List of Figures ••.••••••••.•..••••••••••••.•.••••••••••••••.••••.•.•..••.••••••••••••••.•.•.••••••••••••••••••••••••••••••••• 13 Abbreviations •••••....•••••••••.•...••••••.••••••.•.•••.•...••.••.••••••...•.••••.•...••.•••.•..•••••••.•..••...•...••.••.•• 16 SECTION (I): INTRODUCTION ........................................................ 19 Chapter 1: Benzene •.•••..•••.•..•..•••••••••••••••••..•••.••••••••.••.••••••••••••.•.•.•.•••••••••••.••••••••••.••••..•. 21 1.1.1 Am.btent Concentration ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 22 1.1.2 Sources ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 23 1.1.3 Production ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 26 1.1.4 Uses ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 27 Chapter 2: Benzene Toxicokinetics .•...•.••••••.•....•.•.••••••.•.•..•••••••.••••••.....••••••••••••••.•••••••• 30 1.2.1 Absorption •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 30 1.2.2 Distribution ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 31 1.2.3 Metabolism ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 31 1.2.4 Excretion •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 47 1.2.5 Benzene Toxicity ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 48 Chapter 3: Benzene Biological Markers and Regulations ........................................... 54 1.3.1 Urinary Creatinine •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 54 1.3.2 Benzene Biological Markers •••••••••••••••••••••••••••••••••••••••••••••••••••• 55 1.3.3 Confounding Factors •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 65 1.3.4 Biological Regulations •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 72 SECTION (11): MATERIALS & METHODS ..................................... 75 Chapter 4 :Creatinine Analysis ••••• ~ •••••.••••••.••••••••••••.••.••••..•••••••.•....••••••.•...•..•...•••••••••••• 77 2.4.1 Detennination of Creatinine in Urine ••••••••••••••••••••••••••••••••••••••••• 77 2.4.2 Creatinine Urine Samples •••••••••••••••••••••••••••••••••••••••••••••••••••••••• 77 Chapter 5: Analytical Method for t,t-Muconic Acid in Urine ..................................... 80 2.5.1 HPLC Method ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 81 Chapter 6: Urinary 8-Hydroxy-2'- Deoxyguanosine Analytical Method .................... 86 2.6.1 Materials ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 86 2.6.2 Extraction Procedure •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 87 2.6.3 In.strumentation •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 87 2.6.4 Procedure •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 88 Chapter 7: BTEX Analytical Method ••••••••••••.•••••..•.••••••••••••..••.•••••••••.••••••••••••••••.•.••..•• 91 2.7.1 Instrumentation •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 91 2.7.2 Back and Front Portions of Charcoal Tubes •••••••••••••••••••••••••••••••• 92 2.7.3 Ideal Solvent ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 93 2.7.4 Carbon Disulphide Purification ................................................ 94 2.7.5 Standard Preparation ............................................................... 97 Chapter 8: Monitoring Study Design •••••••••.•••.••••••••.••••••.••.•••••••.••••••••..•••••...••••••••.••••• 102 5 2.8.1 Recruitm.ent of Volunteers ••••••••••••••••••••••••••••••••••••••••••••••••••••• 104 2.8.2 Questionn.aire ••••••••••••••••••• ~ •••••••••••••••••••••••••••••••••••••••••••••••••• 105 2.8.3 Air Samples •••••••••••••••••••••••••••••••••••••••••••••••••••• -;:. •••••••••••••••••• 107 2.8.4 Urine Samples ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 111 SECTION (Ill): RESULTS ................................................................. 114 Chapter 9: Method Development for t,t-Muconic Acid in Urine .............................. 116 3.9.1 Creatinine Level in Urine •••••••••••••••••••••••••••••••••••••••••••••••••••••• 116 3.9.2 t,t-Muconic Acid in Urine •••••••••••••••••••••••••••••••••••••••••••••••••••••• 118 Chapter 10: Urinary 8-Hydroxy-2'- Deoxyguanosine ............................................... 125 3.10.1 Internal Stan.dard •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 126 3.10.2 -8Hydroxy-2'-Deoxyguanosine Recovery ................................ 127 Chapter 11: BTEX in air •••..•••.•....••••••••••••.•.•••••••••••.••...••••••••••••••.••.•.•••••••••••....•••..••.••• 130 3.11.1 CS 2Purification and 13X Regeneration ................................... 130 3.11.2 Mass Fragmentation ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 135 3.11.3 BTEX Measurement in Air •••••••••••••••••••••••••••••••••••••••••••••••••••• 136 Chapter 12: Monitoring of Samples from Car Drivers .............................................. 140 3.12.1 t,t-Muconic Acid in Urine Samples ......................................... 142 3.12.2 Control Group ••. ~ •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 147 3.12.3 Exposed Groups ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 148 3.12.4 In.terindividual Variation ••••••••••••••••••••••••••••••••••• ~ ••••••••••••••••••• 153 3.12.5 Phase 11 •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 153 3.12.6 Potential Confounders ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• 155 3.12.7 t,t-Muconic Acid Distribution in 48 Hours-profile ..................... 166 3.12.8 Follow-up Samples (24-Hour Profile( ..................................... 167 3.12.9 BTEX in Petrol and Diesel Cars ............................................. 180 3.12.10 Urinary t,t-Muconic Acid and Air Sample •••••••••••••••••••••••••••••••• 198 SECTION (IV): GENERAL DISCUSSION ...................................... 202 Future Work ••••••••••••.•••••••••••••••••••••••••.•.•.••••••••••..••••.•••••••.••.••••••.••..•••.••••••.••..•••••••.••..•• 211 APPENDICES ...................................................................................... 212 Appendix I: Urine Data.....•.•••..••...••.....•••.....•...••..••.•••.••..•..•..••.••..•..•...•.••.•..•••..•••.•••.•• 213 Table A .......................................................................................................... 213 TableB ........................................................................................................
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