Table Of ContentArsenic 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
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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
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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
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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
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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
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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
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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
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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
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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
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Description:Chapter 4 Ground water arsenic exposure in Allama Iqbal town Lahore, Punjab, Pakistan .. 80. Abstract . All these samples were transported to Geochemistry lab of SEAES University of Manchester UK CRM (NIES No.18) for human urine analysis were used for assurance of analytical quality.