Arsenic Exposure and Risk Assessment in Allama Iqbal Town, Lahore Pakistan A thesis submitted to The University of Manchester for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences 2011 Seema Anjum Khattak School of Earth Atmospheric and Environmental Science Contents Abstract ................................................................................................................................... 14 Declaration .............................................................................................................................. 16 Copyright Statement ............................................................................................................... 17 Dedication ............................................................................................................................... 18 Acknowledgements ................................................................................................................. 19 The Author .............................................................................................................................. 20 Chapter 1 Introduction ............................................................................................................ 24 Project relevance, goals, approach, and thesis structure ........................................................ 24 Nature and duration of the project ......................................................................................... 28 Aims and objectives............................................................................................................... 31 Project out puts ...................................................................................................................... 32 Thesis Overview .................................................................................................................... 33 References ............................................................................................................................. 37 Chapter 2 Review of Analytical methods for Arsenic / Arsenic Speciation ........................... 40 Introduction ........................................................................................................................... 40 Sampling and analytical technique ........................................................................................ 41 Sample collection .................................................................................................................. 41 Analytical techniques for Total arsenic ................................................................................. 41 Drinking water analysis ......................................................................................................... 41 2 Hair and nail analysis ............................................................................................................ 41 Urine samples analysis .......................................................................................................... 42 Raw rice analysis ................................................................................................................... 42 Exposure and risk calculation ................................................................................................ 43 Statistical analysis.................................................................................................................. 43 Grinding/Milling .................................................................................................................... 45 Extraction methods ................................................................................................................ 45 Detection methods ................................................................................................................. 50 References ............................................................................................................................. 54 Chapter 3 Risk Assessment Methods – A Review.................................................................. 58 Introduction ........................................................................................................................... 58 Risk assessment Methods/Models ......................................................................................... 60 The NAS Model..................................................................................................................... 61 USEPA (2003) Cumulative Risk Assessment Model............................................................ 65 Assessment of potential health risk from combined exposures ............................................. 66 Deterministic point approach................................................................................................. 67 Probabilistic methods ............................................................................................................ 69 Simulation method (Monte Carlo Analysis) .......................................................................... 70 Uncertainty and variability .................................................................................................... 71 Scenario uncertainty .............................................................................................................. 71 3 Parameter Uncertainty ........................................................................................................... 72 Model uncertainty .................................................................................................................. 73 Inter individual variability: .................................................................................................... 74 Spatial variability .................................................................................................................. 74 Temporal variability .............................................................................................................. 74 Conclusion ............................................................................................................................. 74 Chapter 4 Ground water arsenic exposure in Allama Iqbal town Lahore, Punjab, Pakistan .. 80 Abstract .................................................................................................................................. 80 Introduction ........................................................................................................................... 81 Materials and methods ........................................................................................................... 84 The study area ........................................................................................................................ 84 Sampling and analytical technique ........................................................................................ 87 Quality control ....................................................................................................................... 89 Exposure and risk calculation ................................................................................................ 92 Results and discussion ........................................................................................................... 92 Discussion about various steps involved during raw rice cleaning, extraction and analysis 94 Conclusion ........................................................................................................................... 105 References ........................................................................................................................... 106 Supplementary information ................................................................................................. 113 Chapter 5 Role of biomarkers in arsenic exposure assessment due to drinking arsenic contaminated water and eating rice in Allama Iqbal Town Lahore, Pakistan ...................... 120 4 Abstract ................................................................................................................................ 120 Introduction ......................................................................................................................... 121 Material and Methods .......................................................................................................... 123 Sample collection ................................................................................................................ 123 Washing and cleaning procedure ......................................................................................... 124 Digestion and analysis ......................................................................................................... 125 Results and discussions ....................................................................................................... 126 Female population biomarkers data and associations .......................................................... 136 Male population biomarkers data and associations ............................................................. 138 Conclusion ........................................................................................................................... 140 References ........................................................................................................................... 141 Supplementary Information ................................................................................................. 145 Chapter 6 Relationship of Drinking /Cooking water and rice Arsenic contents to Biomarkers of Arsenic exposure in West Bengal India ........................................................................... 148 Abstract ................................................................................................................................ 148 Introduction ......................................................................................................................... 149 Material and Methods .......................................................................................................... 151 Sample collection and cleaning ........................................................................................... 151 Digestion and analysis ......................................................................................................... 152 Results and Discussion ........................................................................................................ 159 5 Association of arsenic in drinking/cooking water and rice (raw & cooked rice) with biomarkers (hair, nail, and urine arsenic) ............................................................................ 161 Conclusion ........................................................................................................................... 172 References ........................................................................................................................... 173 Supplementary information ................................................................................................. 178 Chapter 7 Preliminary study for arsenic exposure and risk assessment in Peshawar Basin of Khyber Pukhtoon Khwa (KPK) province, Pakistan ............................................................. 186 Abstract ................................................................................................................................ 186 Introduction ......................................................................................................................... 186 Peshawar Basin .................................................................................................................... 187 Climatic Condition .............................................................................................................. 188 Population of the field Area ................................................................................................. 188 Methodology ........................................................................................................................ 190 Sampling and Field Survey .................................................................................................. 190 Questionnaire survey ........................................................................................................... 190 Sample collection: ............................................................................................................... 190 Washing and cleaning procedure ......................................................................................... 193 Field analysis ....................................................................................................................... 193 Chemical analysis ................................................................................................................ 193 The quality control measures ............................................................................................... 194 Data analysis and data presentation ..................................................................................... 195 6 Results and discussions ....................................................................................................... 196 Short coming of the study .................................................................................................... 199 Conclusion ........................................................................................................................... 199 References ........................................................................................................................... 200 Supplementary Information ................................................................................................. 202 Chapter 8 Conclusions and future work ......................................................................... 209 Conclusions ......................................................................................................................... 209 Future work.......................................................................................................................... 211 7 List of Figures Figure 1.1 Mean arsenic concentrations in ground water in different districts of Pakistan ......... 27 Figure 1.2 Geological map of Lahore (modified from Geological Survey of Pakistan, Lahore 2008) showing the sample collection points ................................................................................. 30 Figure 2.1 Schematic for Different Analytical Techniques available for As/As-Speciation Analysis after (Hung et al 2004) ................................................................................................... 44 Figure 3.1 Arsenic Exposure Pathways ........................................................................................ 64 Figure 4.1 Administrative boundary map of District Lahore showing different districts (Local Government, 2001) ....................................................................................................................... 85 Figure 4.2 Geological map of District Lahore showing Sampling locations (GSP, 2009) ........... 86 Figure 4.3 Comparison of analysis of duplicate water samples (A and B) for total arsenic (µg/L) ...................................................................................................................................................... 91 Figure 4.4 Distribution of As in drinking water (µg/L) from households of Allama Iqbal Town, Lahore. Box and whisker plot shows inter-quartile range as a box, total range as whisker, with outliers indicated by dots or stars which are included in calculation. .......................................... 94 Figure 4.5 Distribution of total As (mg/L) in raw rice samples collected from Allama Iqbal Town, Lahore ................................................................................................................................ 96 Figure 4.6 Organic (DMA, MMA & As-B) and inorganic species distribution in raw rice from different households units of Allama Iqbal Town, Lahore. . ........................................................ 97 Figure 4.7 Comparison of the results (total As in µg/L) by ICP-MS and HPLC-ICPMS (species sum) .............................................................................................................................................. 98 Figure 4.8 Association of As concentration in drinking water with amount of As concentration in human hair samples from the volunteers of AI Town Lahore (marked by Gender) .................. 101 Figure 4.9 Association of total daily intake with amount of As concentration in human Hair samples from the volunteers of AI Town Lahore (marked by Gender) ...................................... 102 Figure 4.10 Spatial variation of arsenic in drinking water, raw rice, human nails and hair in Allama Iqbal town Lahore .......................................................................................................... 119 Figure 5.1 Arsenic contents in hair samples (µg/g) from male and female population of Allama Iqbal town, Lahore ...................................................................................................................... 127 8 Figure 5.2 Arsenic contents in nails samples (mg/kg) from male and female population of Allama Iqbal town, Lahore ......................................................................................................... 129 Figure 5.3 Total urinary arsenic (µg/L) in urine samples of volunteers (male and female) from Allama Iqbal town Lahore .......................................................................................................... 130 Figure 5.4 Correlation of hair arsenic (mg/kg) and calculated total daily intake CDI (µg/kg/day) for male and female volunteers from Allama Iqbal town Lahore ............................................... 133 Figure 5.5 Associations for As contents in hair, nails, urine, rice, water samples (µg/L) from male and female volunteers from Allama Iqbal town Lahore .................................................... 135 Figure 5.6 Correlation of arsenic in hair with arsenic in nails (mg/Kg) for female volunteers of Allama Iqbal town, Lahore ......................................................................................................... 137 Figure 6.1 Standard deviation of duplicate samples of rice analysed by ICP-MS for total As (mg/Kg) ....................................................................................................................................... 158 Figure 6.2 Total arsenic in rice samples, IC-ICP-MS vs ICP-MS .............................................. 159 Figure 6.3 Graphical representation of correlation values for different parameters (with 95%CI) for all volunteers of West Bengal India ...................................................................................... 166 Figure 6.4 Graphical representation of the correlation between As contents of nails (mg/kg) vs As contents of drinking/cooking water (µg/L) for both male and female population of West Bengal India ................................................................................................................................ 167 Figure 6.5 Graphical representation of the correlation between As contents of hair (mg/kg) vs As contents of drinking/cooking water (µg/L) for both male and female population of West Bengal India ............................................................................................................................................ 168 Figure 6.6 graphical representation of the correlation between As contents of nails (mg/kg) vs As contents of hair (mg/kg) for both male and female population of West Bengal India ............... 169 Figure 6.7 Graphical representation of the correlation between As contents of hair (mg/kg) vs As contents of cooked rice (mg/kg) for both male and female population of West Bengal India ... 170 Figure 6.8 Graphical representation of the correlation between As contents of nails (mg/kg) vs As contents of cooked rice (mg/kg) for both male and female population of West Bengal India .................................................................................................................................................... 171 Figure 6.9 Graphical representation of correlation values for different parameters for female population of West Bengal India ................................................................................................ 183 9 Figure 6.10 Graphical representation of correlation values for different parameters for male population of West Bengal India ................................................................................................ 185 Figure 7.1 Map of Peshawar Basin (including Peshawar, Mardan, Nowshera, Charsadda and Swabi) and the drainage system .................................................................................................. 189 Figure 7.2 Field area and sample location map for Peshawar Basin KPK, Pakistan ............ 192 Figure 7.3 Graphical presentation of association among the log transformed As concentration data for drinking/cooking water, raw rice, biomarkers of As exposure and CDI for Peshawar basin KPK ................................................................................................................................... 203 Figure 7.4 Reproducibility of rice results (sample A vs B) for Peshawar basin, KPK ............... 204 10
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