Biol Trace Elem Res (2016) 173:35–46
DOI 10.1007/s12011-016-0636-0
Arsenic Exposure in Children through Drinking Water
in Different Districts of Sindh, Pakistan
Jameel Ahmed Baig 1 & Tasneem Gul Kazi 1 & Muhammad Ayaz Mustafa 4 &
Imam Bakhsh Solangi 2 & Mirza Junaid Mughal 3 & Hassan Imran Afridi 1
Received: 12 November 2015 / Accepted: 29 January 2016 / Published online: 6 February 2016
# Springer Science+Business Media New York 2016
Abstract A cross sectional study has been conducted during
2007–2010 for the assessment of arsenic (As) contamination
in drinking water, and its impact on the health of local public
belongs to five districts of Sindh, Pakistan. The toxic risk
assessment of As in different areas of Sindh province based
upon its concentration in drinking water and scalp hair of boys
and girls of age group 5–10 and 11–15 years. The total and
inorganic As species in drinking water samples of four dis-
tricts Hyderabad, Sukkur, Naushehro Firoze, Nawab shah,
and Dadu were determined by advance pre-concentration
methodologies. The resulting data indicated that the dominant
inorganic As species in municipal treated (Hyaderabad) and
hand pumps (Sukkur, Naushehro Firoze, Nawab shah and
Dadu) water samples were arsenate (As V ) and arsenite
(AsIII), respectively. The total As concentrations in hand
pumps water samples of Dadu district were 6.0- to 35-fold
higher than the World Health Organization permissible limit
of (10 μg/L) for drinking water. Whereas, total As in hand
pump water samples of Sukkur, Naushehro Firoze, and
Nawab shah were found in the range of 26.0–98.2, 18.0–
* Jameel Ahmed Baig
jab_mughal@yahoo.com
Tasneem Gul Kazi
tgkazi@yahoo.com
Muhammad Ayaz Mustafa
ayazbukero@gmail.com
Imam Bakhsh Solangi
imamsolangi@yahoo.com
Mirza Junaid Mughal
mughal.mirzajunaid@yahoo.com
50.6, and 52.3–85.2 μg/L, respectively. However, municipal
treated water samples of Hyderabad were within recommend-
ed level (As <10 μg/L). The content of total As in children of
both genders and age group belonging to Sukkur, Naushehro
Firoze, Nawab shah, and Dadu was found to be significantly
high as compared to those children residing in Hyderabad
district. The Pearson coefficient of correlation r values be-
tween As levels in hand pump water and scalp hair samples
of children belonging to Sukkur, Naushehro Firoze, Nawab
shah, and Dadu were observed in the range of 0.65–0.75,
0.75–0.82, 0.80–0.90, and 0.95–0.98, respectively. The results
of As toxicity risk assessment based on hazard quotient indi-
cated that Dadu district has high carcinogenic exposure risk
for children. Moreover, it is concluded that the children con-
suming groundwater of Sukkur, Naushehro Firoze, Nawab
shah, and Dadu districts of Sindh, Pakistan were at risk of
chronic As toxicity in future.
Keywords Arsenic toxicity . Drinking water . Scalp hair .
Children . Hazard quotient
Hassan Imran Afridi
hassanimranafridi@yahoo.com
1
National Center of Excellence in Analytical Chemistry, University of
Sindh, Jamshoro 76080, Pakistan
2
Dr. M. A. Kazi Institute of Chemistry, University of Sindh,
Jamshoro 76080, Pakistan
3
Paediatric Department, Peoples University Medical and Health
Sciences, Nawabshah, Pakistan
4
PMRC Specialized Research Centre on Child Health, National
Institute of Child Health, Karachi 75500, Pakistan
36
Introduction
The contaminated drinking water with arsenic (As) is one of
the serious public threat, either derived from anthropogenic
and/or geological sources [1–8]. The exposure of As by drink-
ing water was reported in Taiwan, Argentina, Chile, Mexico,
India, Bangladesh, China, Vietnam, and Cambodia [5–9]. The
chronic exposure of oral As toxicity was currently observed in
different areas of Pakistan due to the consumption of As-
contaminated surface and ground water [10–15]. The most
common sign of As exposure is hyper pigmentation especially
on the trunk and keratosis on the palms and soles of the feet.
These skin lesions are generally developed within 5–10 years
after exposure commence, although shorter latencies are pos-
sible [6, 16–19]. Many other signs and symptoms have also
been reported in Bangladesh, i.e., chronic cough, crepitating
in the lungs, diabetes mellitus, hypertension, and weakness
[20, 21].
Inorganic arsenic species arsenite (H2AsO3 ) BAsIII^ and
arsenate (H2AsO4 ) BAsV^are considered to be the major form
of As in drinking water, soil, and food commodities [22, 23].
Thus, for more appropriate information about the toxicologi-
cal significance, it is necessary to assess different As species
[24]. For the speciation of inorganic As, the separation and
pre-concentration methods reported in the literature are usual-
ly based on hydride generation, solid phase extraction, cloud
point extraction, co-precipitation, ion exchange, chromatogra-
phy, and capillary electrophoresis [25–29]. Among them, the
cloud point extraction (CPE) technique was used for the ex-
traction of inorganic As (iAs) species (AsIII and AsV), based
on the phase separation of non-ionic surfactants in aqueous
media [15, 18, 30, 31]. For the determination of total iAs, the
enrichment on solid phase (sorbent) from liquid phase (sample
solution) is used [28, 32]. These sample pre-concentration
methodologies are simple, low cost, environmental friendly,
and provide high pre-concentration factor [15, 28, 32].
The iAs in drinking water is generally found in >95 % of
total As, which may have capability to absorb easily in the
gastrointestinal tract [33, 34]. About 50–70 % As absorbed As
in the gastrointestinal tract and lungs through inhalation and
ingestion may be excreted from body through urine [16, 17].
The residual absorbed As in human body tends to accumulate
in keratinized tissues, such as skin, hair, and nails [13, 16].
The hairs may be provided long-term history and information
of chronic As exposure due to their high biological stability
[35]. Moreover, numerous studies have shown that As con-
centrations in hair may have good association with As con-
tents in drinking water [13, 33, 35, 36]. Thus, human hairs
have been extensively used as biomarker for for the quantifi-
cation of As contents during human epidemiological studies
[35, 37].
The objective of this study was to evaluate the cumulative
exposure of As via drinking water and its correlation with As
Baig et al.
levels in scalp hair of children and calculated As toxic risk
factors in Hyderabad, Sukkur, Naushehro Firoze, Nawab
shah, and Dadu. The total, inorganic, pentavalent, and triva-
lent As species were determined in drinking water of these
regions, while total As in scalp hair samples of boys and girls
of two age groups (6–10 and 11–15 years) were analyzed for
As toxicity risk assessment. The influence of different factors,
i.e., As concentration in municipal treated and groundwater,
period of water consumption, age, and body mass index were
estimated. The correlation of As in drinking water and scalp
hair samples of boys and girls were also studied.
Experimental Work
Water Sampling
The representative hand pump samples at the depth > 15 m
were collected during 2007–2010 from Sukkur, Naushehro
Firoze, Nawab shah, and Dadu districts of Sindh, Pakistan
(n = 200; 50 samples from each district) and map of sampling
districts is shown in Fig.1. For comparative purposes, the rep-
resentative municipal treated water samples (n = 70) were
collected from Hyderabad, Pakistan. The collected water sam-
ples were kept in well-stoppered polyethylene plastic bottles,
which were previously soaked in 10 % nitric acid for 24 h and
rinsed with ultrapure water obtained from ELGA LabWater
system. All water samples were stored in an insulated cooler
containing ice and delivered on the same day to the laboratory
and kept at 4 °C until processing and analysis [9]. The analysis
of AsT total iAs and AsIII were accomplished on the same day
to avoid the risk of transformation of species as reported else-
where [38].
Study Population
The representative scalp hair samples of boys and girls
(n = 337) were simultaneously collected from the same sam-
pling sites of district Sukkur, Naushehro Firoze, Nawab Shah,
and Dadu Sindh, Pakistan. The selected populations of boys
and girls were divided into two age groups 6–10 and 11–
15 years (Table 1). The study population of boys and girls of
district Sukkur, Naushehro Firoze, and Nawab Shah have no
apparent arsenicosis symptom. However, among the represen-
tative boys and girls of Dadu district, about 65 % of elder age
group boys and girls have raindrop pigmentation on the face,
palms of the hands, and soles of the feet. While younger group
boys and girls of Dadu district have rough and dry skin. For
comparative purposes, the scalp hair samples referent boys
and girls (n = 145) residing in Hyderabad district, consuming
municipal treated water were also collected. Total number of
male children of two different age group 6–10 and 11–15 years
of study population are summarized in Table 1. The body
Arsenic Exposure in Children through Drinking Water 37

Fig. 1 Map of study districts of Sindh, Pakistan

mass indexes of boys and girls belonging to district Sukkur,
Noshehro Feroz, Nawab Shah, and Dadu were less than the
recommended value, indicated the malnutrition and poor
health. Cross-sectional epidemiological studies are particular-
ly useful for establishing prevalences and identifying under-
lying risk factors.
Ethical approval was provided by the participating institu-
tions, and permission to conduct the scalp hair sampling has
been undertaken by the head of government basic health cen-
ter of each district. The boys and girls, who gave their consent,
were recruited for scalp hair sampling. Participating boys and
girls did not receive incentives. An information sheet accom-
panied each questionnaire outlining the research aims and
Table 1 Scalp hair sampling statistics for different districts of Sindh
District 6–10 years 11–15 years Total
objectives. Moreover, all study population (boys and girls)
were informed that participation was voluntary and anony-
mous. Before the start of this study, each participant was also
informed about the motive of study in local language (Sindhi)
with the assistance of a local non-government organization
BYoung Welfare Society, Sindh^. The sociodemographic in-
formation (e.g., gender, age), nutrition, dietary intake, and
food consumption patterns, as well as the importance of
healthy eating, three levels of physical activity, restful sleep,
tobacco smoking, use of illicit substance (recreational drugs),
frequency of binge drinking, and drinking problem, has been
collected. All the outcomes were examined according to As
levels in the drinking water and scalp hair of each participant.
The scalp hair samples were collected from the nape of the
head using stainless steel scissors. Hair samples were sealed
separately in labeled polyethylene zip-lock bags and were not
opened until return to the laboratory.

Boys Girls Boys Girls

Reagents and Materials
Hyderabad 12 17 16 20 65
Dadu 15 20 14 16 65 Ultrapure water (resistance 0.05 μS/cm) obtained from an
Sukkur 15 18 18 20 71 ELGA LabWater system (Bucks, UK) was used throughout
Naushehro Firoze 19 15 17 21 72 the experiment. Concentrated HCl (purity 37 %, sp. gr. 1.19)
Nawab Shah 14 12 20 18 64 and H2O2 (purity 30 %, sp. gr. 1.11) were of analytical reagent
grade and were obtained from Merck (Darmstadt, Germany).
38
Ammonium pyrrolidinedithiocarbamate (APDC) obtained
from Fluka Kamica (Buchs, Switzerland) was used as the
chelating agent to form the hydrophobic metal complexes.
The APDC solution (0.1 % w/v) was prepared by dissolving
a suitable amount of APDC in ultrapure water. Titanium (IV)
dioxide (purity 99 %, Merck) was used as a sorbent.
The stock standard solution of iAsIII at a concentration of
1000 mg/L was prepared by dissolving of As2O3 (Merck) in
1.0 mol/L KOH and adjusting the pH to 7.0 with 10 % HCl.
While the working standard solutions for As analysis by atom-
ic absorption spectrometry were prepared by dilution of certi-
fied standard solution (1000 mg/L) in 0.2 M HNO3 obtained
from Fluka Kamica (Buchs, Switzerland). Triton X-114
Sigma (St.Louis, MO, USA) was used as the non-ionic sur-
factant. Appropriate dilutions were made from this solution
with 1.0 M HCl whenever required. The chemical modifier
Mg(NO3)2 stock standard solution, 2000 mg/L, was prepared
from Mg(NO3)2 (Merck), and Pd stock standard solution,
3000 mg/L, was prepared from Pd 99.999 % (Aldrich,
Milwaukee, WI, USA). For the accuracy of methodology,
certified reference materials (CRMs) of human hair BCR
397, BCR (Brussels, Belgium), and water SRM 1643e,
NIST (Gaithersburg, MD, USA) were used. All glass wares
and polyethylene bottles were thoroughly washed and soaked
overnight in 5.0 mol/L HNO3 and were thoroughly rinsed
with distilled and de-ionized water before use.
Apparatus
WIROWKA Laboratoryjna type WE-1, nr-6933 centrifuge
(speed range 0–6000 rpm, timer 0–60 min, 220/50 Hz;
Mechanika Phecyzyjna, Poland) was used for centrifugation.
A mechanical shaker (Gallenkamp, UK) was used for shaking.
The pH was measured by a pH meter (781 pH meter;
Metrohm). A global positioning system (GPS) iFinder
(Lowrance, Mexico) was used for sampling locations (Fig 1).
The As was determined by a double-beam Perkin Elmer
(Norwalk, CT, USA) atomic absorption spectrophotometer
equipped with a graphite furnace HGA-400, autosampler
AS-800, and deuterium lamp for background correction used
for quantitative analysis of tAs, iAs, and their species. Single-
element hollow cathode lamp of As operated at 7.5 mA was
used as energy source. The As signal was isolated at 193.7 nm
with a spectral bandwidth of 0.7 nm, and atomization was
achieved in a pyrocoated graphite tube with integrated plat-
form. WinLab 32 software was used to acquire and process
analytical data. The graphite furnace heating program was set
for different steps for As analysis as drying temperature (°C)/
ramp/hold(s) (140/15/15), ashing temperature (°C)/ramp/
hold(s) (1300/10/20), atomization temperature (°C))/ramp/
hold (2300/0/5), cleaning temp. (°C)/ramp/hold(s) (2600/1/
3). For all determinations, argon (200 ml/min) was used as a
purge gas except during the atomization step. Ten microliter of
Baig et al.
standards/samples and 10 μl modifier (5 μg Mg(NO3)2 + 3 μg
Pd) were injected into the electrothermal graphite atomizer.
Integrated absorbance signals computed by the AA spectrom-
eter were employed throughout.
Determination of Total As (AsT)
Duplicate water samples collected from each site were treated
according to US EPA Method 3015 [39, 40]. For quality con-
trol purposes, the Standard Reference Water, SMR1643e
(NIST, Gaithersburg, MD) was used. The average recovery
was 98.9 % and the percentage relative deviation was below
1.48 % [4, 39].
Determination of Total Inorganic Arsenic and its Species
Total iAs and AsIII were determined by solid phase and cloud
point extractions methods, respectively. The detail about the
determinations of total iAs and AsIII were reported in our
previous work [31, 41]. The concentration of AsV could not
be determined directly according to the above analytical pro-
cedure, but its concentration was estimated as the difference of
total iAs and AsIII.
Preparation of Scalp Hair Samples
The scalp hair samples were cut into small pieces (2 cm) and
washed as proposed by the International Atomic Energy
Agency prior to analysis. The hair samples were successively
washed with ultrapure water, three times with acetone, and
finally with ultrapure water (three times). The samples were
then oven dried at 60 °C. After drying duplicate samples of
scalp hair (200 mg), each subject was directly taken in PTFE
flasks (25 mL in capacity). About 2 mL of a freshly prepared
mixture of concentrated HNO3–H2O2 (2:1, v/v) was added to
each flask and kept for 10 min at room temperature, and then
the flasks were placed in a covered PTFE container, then heat-
ed following a one-stage digestion program at 80 % of total
power (900 W). Complete digestion of scalp hair samples
required 2–4 min. After the digestion, the flasks were cooled
at room temperature and the resulting solutions were evapo-
rated to semidried mass to remove excess acid. About 5 mL of
0.1 M nitric acid was added to the residue and filtered through
a Whatman no.42 filter paper and diluted with deionized water
up to 10 mL in volumetric flasks. Blank extractions were
carried out through the complete procedure. Blanks and stan-
dard solutions were prepared in a similar acid matrix. The
validity and efficiency of the microwave assisted digestion
method was checked with certified values of CRM BCR-
397 of human hair.
Arsenic Exposure in Children through Drinking Water
Arsenic Risk Assessment
Arsenic risk factor has been calculated for non-
carcinogenic exposure, as hazard quotient (HQ) can be
calculated as [42, 43]:
HQ ¼ EDI=R f D
where RfD is the oral toxicity reference value for As
equal to 3.04E − 04 mg/kg/day, and the estimated daily
intake dose (mg/kg/day) calculated as [42]:
EDI ¼ ðC  IR  EF  EDÞ=ðBW  ATÞ
where EDI is the estimated daily intake (mg/kg/day), C
is the As concentration in water (mg/L), IR is the intake
rate (L/day), EF is the exposure frequency (d/year), ED
is the exposure duration (year), BW is the body weight
(kg), and AT is the average age time (d).
If the calculated HQ is <1, then no adverse health effects
are expected, while >1, adverse health effects are possible
[42]. Body weights were obtained by weighing each individ-
ual on a body weight scale.
Carcinogenic Risk Assessment
Carcinogenic risk factor is the probability of an incidence of
chronic diseases from chemical exposure and can be comput-
ed as reported in previous study [16, 17, 36]:
R = 1 − 10[−(SF × EDI)].
Where SF is the oral slope factor. Toxicity data for thresh-
old and non-threshold effects from As exposure are available
from the USEPA database, Integrated Risk Information
System [43, 44]. The oral slope factor (SF) for As in skin
cancer is 1.5 (mg/kg/day) [42, 43].
Statistical Analysis
Data processing and statistical analysis were conducted by
using computer program Excel (Windows XP 2007;
Microsoft Corp., Redmond, WA, USA) and Minitab 13.2
(Minitab Inc., State College, PA, USA) software packages.
Normally distributed data were expressed as means ± standard
deviation and Student’s t test were used to assess the signifi-
cance of the differences between the As content in scalp hair
of children exposed to different levels of As via drinking wa-
ter. All tests were two sided and a p value of ≤0.05 was con-
sidered significant. Pearson product-moment correlation coef-
ficients were calculated to test linear correlations between As
contents in hair and water. The average daily intake of As was
calculated according to the volume of water consumed per
day.
39
Analytical Figure Merit
The calibration graph was obtained for the determination of
iAsIII and total iAs by electrothermal atomic absorption spec-
trometry. The calibration graph for iAsIII and AsT was linear
with a correlation coefficient of 0.9999 and 0.998, respective-
ly, at quantification limit up to 20 μg/L. The LOD values were
0.05 and 0.22 μg/L and LOQ 0.12 and 0.63 μg/L for iAsIII and
total iAs, respectively.
Due to the unavailability of reference material for As spe-
ciation, the validity of the analytical method was performed on
three replicate sub-samples of a municipal treated tap water,
spiking with iAsIII and total iAs at three concentrations level,
then applying both methods. The recoveries for iAsIII and total
iAs were generally greater than 98 % (Table 2). A good agree-
ment was obtained between the added and measured analyte
concentrations. In order to validate the method for total arse-
nic, certified reference materials SRM 1643e (water) and BCR
397 (human hair) were analyzed. The average recovery was
>97 % and the percentage coefficient of variation were <5 %
(Table 2).
Result and Discussion
The AsT concentration in the hand pump water samples of
Sukkur, Naushehro Firoze, Nawabshah, and Dadu districts
of Sindh, Pakistan was observed in the range of 26.0–98.2,
18.0–50.6, 52.3–85.2, and 63.5–345 μg/L, respectively
(Table 3). The contents of AsT in hand pump samples of
districts Sukkur and Dadu were 3–10 and 6.0–34.5 times
higher than WHO permissible limits of As in drinking water,
respectively. Whereas, the hand pump water samples of
Sukkur and Nawabshah have moderate As contaminaton.
The levels of AsT in hand pump samples of Sukkur and
Nawabshah were 2 to 8 times higher than WHO recom-
mended levels for drinking water (As = 10 μg/L). The AsT
concentration in municipal treated water samples of district
Hyderabad were within WHO recommended levels for
drinking water [45]. The AsT concentrations in hand pump
water samples of Sukkur, Naushehro Firoze, and Nawabshah
districts were comparable than those reported in groundwa-
ter samples by Arain et al. (2009) in Jamshoro district
(23.30–96.30 μg/L), Nickson et al. (2005) in Muzaffargarh
district (1.00–905 μg/L) and Farooqi et al. (2007) in Lahore
and Kasur district (10.00–1900 μg/L). The hand pump sam-
ples of Dadu district have higher contents of AsT as com-
pared to reported districts of Pakistan [11, 12, 38]. This
might be due to several natural sources, e.g., geothermal,
geo-hydrological, and bio-geochemical factors [23, 46].
Moreover, the hot climate of Dadu district may be one of
predominate factor, which may lead to increase the evapo-
ration rate. Thus, this factor may be leading contributor for
40 Baig et al.

Table 2 Determination of arsenic

in certified samples (n = 6) and Species Added concentration Mean ± SD (μg/L) % Recovery
standard addition method for (μg/L)
validation of extractions methods
for inorganic arsenic species (iAs) iAsIII 0.00 1.18 ± 0.12 –
2.5 3.63 ± 0.15 98.4
5.0 6.12 ± 0.24 99.0
10.0 11.1 ± 0.17 99.3
Total iAs 0.00 4.4 ± 0.28 –
2.5 6.83 ± 0.15 98.9
5.0 9.31 ± 0.19 99.0
10.0 14.26 ± 0.35 99.0
Total As (mg/L or mg/kg) method validation
Certified samples Certified values MDM % Recoverya texperimetal value
tcriticalb
Water (SRM 1643e) 60.45 ± 0.72 59.9 ± 0.89 (1.39)c 99.1 0.309
Human hair mg/kg 0.31 ± 0.02 0.305 ± 0.014 (4.59)c 98.4 0.515
(BCR 397)
a
% recovery = [experimental value]/[certified value] × 100
b
t (critical) at 95 % CI = 2.57, p = 0.05, DF = 5
c
Values in parenthesis RSD

the elevated concentration of AsT in Dadu district groundwa-
ter along with high contents of dissolved solids [19, 38, 39].
The toxicological behavior and biochemical activity of As
most commonly depends on its chemical form. The AsIII is
more toxic and mobile than AsV [15]. It is because of its ability
to form complex with certain co-enzymes associated with bi-
ological activity and dissolved organic water in natural water
[15]. So, the distribution of As species in drinking water is
important. In this context, the speciation of As in hand pump
and municipal treated water samples has been conducted. The
organic As compounds are less available than inorganic As in
hand pump water samples of Sukkur, Naushehro Firoze,
Nawabshah, and Dadu districts. This might be due to the low-
er solubility and natural abundance organoarsenicals in aqui-
fer water [15]. The concentrations of iAs, AsIII, and AsV in
drinking water samples of studied districts are shown in
Table 4. The iAs, AsIII, and AsV in the hand pump water
samples of Sukkur, Naushehro Firoze, Nawabshah, and Dadu
districts were observed (25.0–93.3, 11.5–43.2, and 13.5–
50.1), (17.6–49.1, 9.00–21.7, and 8.70–27.3), (50.2–83.5,
24.1–37.5, and 26.1–46.0), and (61.6–335, 26.7–148, and
35.0–186) μg/L, respectively. Whereas, the concentrations
of iAs, AsIII, and AsV in municipal treated water samples of
district Hyderabad were found in the range of 6.34–9.87,
3.68–7.08, and 1.42–5.27 μg/L, respectively. The obtained
results showed some significant differences (p > 0.05) among
the concentration of inorganic species of As in hand pump
water of all studied districts (Table 4). The contents of iAs
were about 95–98 % of AsT in hand pump water samples of
all studied districts (Tables 3 and 4). The high level of inor-
ganic As species in hand pump samples of all districts might
be due to dissolution of settled down As bearing compounds,
coming from the Himalayas via Indus River throughout the
years [15, 38]. It has been observed that the AsV was leading
inorganic species as compared to AsIII in hand pump water
samples of Sukkur, Naushehro Firoze, Nawabshah, and Dadu
districts (Table 3). The elevated levels of AsV in studied hand
pump water samples might be due to high concentrations of

Table 3 Analytical results of

total As in drinking waters and District Water (μg/L) Scalp hair (mg/kg)
scalp hair of children of two age
groups of different districts Boys Girls Boys Girls
6–10 years 11–15 years

Hyderabad 6.51–9.98 0.15–0.28 0.18–0.32 0.25–0.40 0.23–0.38

Sukkur 26.0–98.2 0.22–0.34 0.18–0.35 0.28–0.45 0.30–0.50
Naushehro Firoze 18.0–50.6 0.34–0.56 0.37–0.53 0.34–0.60 0.30–0.62
Nawab Shah 52.3–85.2 0.40–0.92 0.38–0.94 0.42–0.96 0.50–1.02
Dadu 63.5–345 4.50–8.20 6.00–8.90 7.50–10.20 6.80–9.52
Arsenic Exposure in Children through Drinking Water 41

Table 4 Analytical results of inorganic As in drinking waters of 15 years of Dadu districts were at high risk of arsenicosis due
different districts
to continuous consumtion of As contaminated ground water.
District Arsenic species Water (μg/L) Whereas, there was no apparent effects of As exposure ob-
served in boys and girls of both age groups belonging to
Hyderabad AsIII 3.68–7.08 Sukkur, Naushehro Firoze, and Nawabshah districts, although
AsV 1.42–5.27 the level of AsT in scalp hair samples was found to be higher
iAs 6.34–9.87 than boys and girls of both age groups belonging to district
Sukkur AsIII 11.5–43.2 Hyderabad. These finding are in accordance with other studies
AsV 13.5–50.1 [4, 6, 15, 16, 18–20, 35, 48].
iAs 25.0–93.3 The resulting data shows that the AsT levels in scalp hair of
Naushehro Firoze AsIII 9.00–21.7 boys and girls, age ranged 11–15 years, were found to be
AsV 8.70–27.3 higher as compared to the younger age group (6–10 years)
iAs 17.6–49.1 in all understudy areas. This might be due to high ingestion
Nawab Shah AsIII 24.1–37.5 rate of As containing drinking water (2.0 L) for longer time
AsV 26.1–46.0 period in elder age group [17, 36]. The children are more
iAs 50.2–83.5 susceptible to toxicant including As [13]. It is a commonly
Dadu AsIII 26.7–148 known reality that the continuous growth in childern with
AsV 35.0–186 respect to increase in age needed more nutrients. Thus, they
iAs 61.6–335 consume more food per unit body weight than the adults and
the excretion also varies with maturation of the kidney and
other systems [2, 13, 17]. Thus, in addition to high levels of As
HCO3 (>500 mg/L), SO42- (>250 mg/L), and pH > 7.5 under through drinking water, other local food commodities may
oxidizing environment [5, 21, 41, 46]. All this provides evi- have contribution in exposure of As toxicity [49–56].
dence that the anthropogenic and geological environment Thus, the correlation of AsT in scalp hair samples of boys
plays a key role in the distribution of studied inorganic As and girls of two age groups residing in Hyderabad, Sukkur,
species in water bodies of the areas under study. Naushehro Firoze, Nawabshah, and Dadu districts with the
The concentrations of AsT in scalp hair of boys and girls of AsT levels of corresponding drinking water has been comput-
two age groups (6–10 and 11–15 years) of five districts of ed (Table 5). The significantly higher correlation (r = 0.86–
Sindh Pakistan are given in Table 3. The concentration of 0.89, p < 0.001) of AsT concentrations in hand pump water
AsT in scalp hair samples of boys and girls (age groups 6–10 samples with the AsT in scalp hair of boys and girls of both age
and 11–15 years) was significantly higher in Dadu district groups belonging to district Dadu were observed as compared
ranged from (0.15–0.28 and 0.25–0.40) to (0.18–0.32 and to other studied districts of Sindh, Pakistan (p > 0.01). The
0.23–0.38) mg/kg, respectively. The contents of AsT scalp hair good correlation has been found between AsT contents in
of girls of age group 6–10 and 11–15 years of Sukkur, drinking water and scalp hair samples of boys and girls of
Noshehro Feroz, and Nawabshah districts were higher than both age groups of districts Sukkur, Naushehro Firoze, and
boy subjects belonging to same areas. However, the difference Nawabshah (r = 0.670–0.741, r = 0.771–0.829, and
was not significant (p < 0.01). The boy and girl subjects of r = 0.820–0.859, p < 0.05, respectively). The weak correlation
both age and gender groups who belong to the Hyderabad has been observed between AsT concentration in municipal
district consuming municipal treated water had significantly treated water and scalp hair of studied population both gender
lower AsT concentration in scalp hair samples as compared to and age groups (r < 0.500; p > 0.05).
boys and girls belonging to other studied districts (p > 0.01). However, the food and water were considered to be major
The AsT levels in scalp hair samples of (Sukkur, Naushehro sources of As as well as with background exposures from
Firoze, and Nawabshah) indicated that the population was at inhalation of airborne particles or ingestion of soils being neg-
risk of moderate As toxicity. Whereas, the study subjects be- ligible in the general population [57]. The Agency for Toxic
longing to Dadu district were at risk of high risk of As toxicity. Substances and Disease Registry in 2000 demonstrated that
However, the level as the AsT levels in scalp hair of boys and As can enter the human body via several pathways, but all
girls of both age groups belonging to Hyderabad districts was other intake routes of As are usually negligible in comparison
within the recommended values of AsT 0.080 to 0.250 mg/kg to oral intake [58, 59]. Thus, the estimated daily intake dose
in human hair [47]. (EDI) of As through drinking water (municipal treated and
The high exposure of As in boys and girls of both age hand pumps water) was calculated to assess the As intake at
groups of district Dadu had As-induced skin disorders as com- different levels. The boys and girls of Sukkur, Naushehro
pared to boys and girls of other studied districts (p > 0.01). It is Firoze, Nawabshah, and Dadu districts were equally and con-
expected that the boys and girls of age group 6–10 and 11– tinuously exposed to As contaminated drinking water
42 Baig et al.

Table 5 Linear regression and

Pearson coefficient in between District AsT in drinking water versus AsT in scalp hair
total As in scalp hair samples of
children of two age groups (6– Boys Girls Boys Girls
10 years and 11–15 years) versus 6–10 years 11–15 years
total As in drinking water of three
understudy areas Hyderabad y = 0.027x + 0.044 y = 0.028x − 0.069 y = 0.026x + 0.089 y = 0.03x + 0.050
r = 0.450 r = 0.435 r = 0.474 r = 0.494
Sukkur y = 0.001x + 0.193 y = 0.001x + 0.157 y = 0.001x + 0.273 y = 0.002x + 0.268
r = 0.670 r = 0.708 r = 0.689 r = 0.741
Naushehro y = 0.007x + 0.244 y = 0.004x + 0.295 y = 0.006x + 0.284 y = 0.008x + 0.178
Firoze r = 0.829 r = 0.771 r = 0.774 r = 0.806
Nawab Shah y = 0.014x − 0.291 y = 0.015x − 0.268 y = 0.016x − 0.401 y = 0.014x − 0.201
r = 0.820 r = 0.859 r = 0.845 r = 0.846
Dadu y = 0.001x + 4.841 y = 0.001x + 5.793 y = 0.0001x + y = 0.0001x +
r = 0.962 r = 0.975 7.493 6.997
r = 0.955 r = 0.976

throughout their lives. The mean concentration of As in drink-
ing water can be used to calculate EDI by multiplying As
concentration of drinking water with daily intake volume.
Information on individual water consumption history in study
population including drinking water sources (ground and mu-
nicipal treated drinking water) has to be collected based on
verbal questionnaire. The water consumption is definitely in-
fluenced by other factors, for example, weather (air tempera-
ture and humidity) and labor intensity, in addition to body size
of study subjects. It has been noted that the all study districts
have hot weather (up to 45 °C). Thus, the intake rate (IR)
assumed as an average 1.5 and 2.0 L/day for young and elder
children, respectively. Whereas, the other parameters, expo-
sure frequency (EF) based on 365 days/year, average exposure
duration (ED) of 7.5 and 12.5 years for 6–10 and 11–15 years,
respectively, mean value of body weight (BW), and mean life
time were used for the calculation of EDI (Table 6).
The daily burden of As from drinking water is a better
index for the estimation of As exposure, expressed in mg/kg
of body weight/day (Table 6). The intake of AsT through hand
pumps water by the community of the study districts exceeded
2 to 340 times than the WHO permissible limit (10 μg/L) for
AsT in drinking water [45]. Thus, the children were at risk as
reported in literature that the increased prevalence of skin
diseases has been observed even at the exposure levels in
the range of 5–10 μg/L As in drinking waters [60, 61].
The HQ and CR values, calculated on the bases of EDI,
have been summarized in Table 6. As estimated daily intake of
tAs, the average HQ values for children of age group 6–
10 years belonging to Hyderabad, Sukkur, Naushehro
Firoze, Nawabshah, and Dadu districts were 0.23, 1.69,
0.99, 1.92, and 5.91, respectively, while the mean CR values
for Hyderabad, Sukkur, Naushehro Firoze, Nawabshah, and
Dadu districts were estimated as 0.001, 0.008, 0.004, 0.009,
and 0.0236, respectively. Whereas in elder age group (11–
15 years), belonging to Hyderabad, Sukkur, Naushehro
Firoze, Nawabshah, and Dadu districts, the HQ and R were
calculated as (0.26, 1.64, 0.96, 1.86, and 4.79) and (0.001,
0.007, 0.004, 0.008, and 0.0196), respectively. On the bases
of these findings, the children of both age groups consuming
hand pumps water of Dadu and Nawabshah districts, Sindh,
Pakistan, have high risk for chronic toxicity of As, which was
indicated by HQ values >1. The estimated CR index values
shows that cancer risk was in order of Dadu > Nawabshah >
Sukkur > Naushehro Firoze > Hyderabad districts. According
to US EPA standards, the guidelines value is less than or equal
to one in a million (1xE-06) [22, 36, 43]. Thus, the high CR
values in studied districts indicated that the children of both
age group were at the risks of different cancer in future. The
CR index of study area was higher than those reported by
Muhammad et al. (2010) for drinking water in Kohistan re-
gion, northern Pakistan, and consistent with Karim (2000) and
Nguyen et al. (2009) for drinking water in Bangladesh and
Vietnam, respectively [36, 44, 62]. The results of water in
Dadu district showed that water has high level of As contam-
ination and is not safe for drinking and other domestic uses.
The clinical investigations indicate that chronic As toxicity
induces harmfully to various organs of the human [34, 63].
The examined subjects belonging to Sukkur, Naushehro
Firoze, and Nawabshah districts have no remarkable derma-
tological symptoms while in elder children belonging to Dadu
district have raindrop pigmentation on the face, palms of the
hands, and soles of the feet. Some chronic symptoms, such as
cramps in the leg muscles, breathing, and gastrointestinal
problems, were also observed. While younger group of chil-
dren of Dadu district have only rough and dry skin. Due to
high rate of illiteracy (90 %) with remarkable poverty, the
parents of studied children belonging to Dadu district used
some ancestral customs for treating any sickness using tradi-
tional treatments. Skin lesions are one of the most common
Table 6 Environmental risk assessment in different district of Sindh, Pakistan

Hyderabad Sukkur Naushehro Firoze Nawab Shah Dadu

6–10 years 11–15 years 6–10 years 11–15 years 6–10 years 11–15 years 6–10 years 11–15 years 6–10 years 11–15 years

IR (L/day) 1.5 2.0 1.5 2.0 1.5 2.0 1.5 2.0 1.5 2.0
Arsenic Exposure in Children through Drinking Water

AsT in Water Min. 0.0065 0.026 0.018 0.052 0.063

(mg/L)
Mean 0.008 0.06 0.035 0.068 0.167
Max. 0.010 0.098 0.051 0.085 0.345
ED Years 7.5 12.5 7.5 12.5 7.5 12.5 7.5 12.5 7.5 12.5
EF Days 365 365 365 365 365 365 365 365 365 365
BW kg 17.0 20.0 17.5 24.0 17.5 24.0 17.5 24.0 14.0 23.0
AT Days 2738 4563 2738 4563 2738 4563 2738 4563 2738 4563
ADD of AsT Min. 5.74E-04 6.50E-04 2.23E-03 2.17E-3 1.54E-03 1.50E-03 4.48E-03 4.36E-03 6.80E-03 5.52E-03
(mg/kg/day) Mean 7.06E-04 8.00E-04 5.14E-03 5.00E-3 3.00E-03 2.92E-03 5.83E-03 5.67 E-03 1.80E-02 1.46E-02
Max. 8.81E-04 9.98E-04 8.42E-03 8.18E-3 4.34E-03 4.22E-03 7.30E-03 7.10E-03 3.70E-02 3.00E-02
HQ Min. 0.19 0.21 0.73 0.71 0.51 0.49 1.47 1.43 2.24 1.82
Mean 0.23 0.26 1.69 1.64 0.99 0.96 1.92 1.86 5.91 4.79
Max. 0.29 0.33 2.77 2.69 1.43 1.39 2.40 2.34 12.16 9.87
CR Min. 8.60E-04 9.75E-04 3.34E-03 3.24E-03 2.31E-03 2.25E-03 6.70E-03 6.52E-03 1.02E-02 0.86E-02
Mean 1.06E-03 1.20E-03 7.68E-03 7.47E-03 4.49E-03 4.36E-03 8.71E-03 8.46E-03 2.36E-02 1.96E-02
Max. 1.32E-03 1.50E-03 12.5E-03 12.2E-03 6.48E-03 6.31E-03 10.9E-03 10.6E-03 4.26E-02 3.62 E-02

IR intake rate, ED exposure duration, BW body weight, AT average age time, HQ hazard quotient, AT average time, ADD average daily intake dose, CR cancer risk
43
44
features of chronic As poisoning, and these symptoms are
used as a diagnostic criteria of endemic As poisoning in inner
Mongolia, China, and other parts of world [5, 35, 37, 64, 65].
The ground water is a major source of drinking water in
Pakistan (Pakistan; Strategic Country Environmental
Assessment Report, 2006). However, several patients in
Pakistan were suffering from water-related bacterial diseases
such as typhoid,
cholera, dysentery, and hepatitis [22, 66, 67]. Malnutrition
and poor socioeconomic conditions of villagers of the
understudied area make worse the hazards of As toxicity.
Although arsenicosis is not an infectious, contagious, or he-
reditary disease, but it creates many social problems for the
victims and their families [68]. Apparently, As contamination
in groundwater presents significant threats to human health in
the local communities of Sukkur, Naushehro Firoze,
Nawabshah, and Dadu districts. Nevertheless, ground water
has been widely used due to the lack of clean water resources
in Sukkur, Naushehro Firoze, Nawabshah, and Dadu districts.
However, other water sources in studied districts were inade-
quate for the execution of the local driking water demands. All
these facts demonstrated that the chronic As poisoning is due
to chronic administration of high concentration of As through
contaminated ground water. Immediate stoppage of As con-
taminated drinking water and the intake of As safe drinking
water are the precondition for the management of chronic As
poisoning.
Conclusion
It has been concluded that the major non-occupational con-
tributors to elevated scalp hair As levels in children of Sukkur,
Naushehro Firoze, Nawabshah, and Dadu districts are due to
As contaminated ground water. It appears to be creating del-
eterious effects on the health of elder age group. The positive
linear regressions showed As concentrations in water versus
SH of boys and girls of age 11–15 years were higher than As
levels in water versus SH of boys and girls of age 6–10 years.
While the As contents in boys of 11–15 years were found
higher as compared to the girls of same age group. This could
be attributed to higher sensitivity of children to the As, might
be due to their large surface-area-to volume ratios, which en-
hanced uptake of As from drinking water. Clinical complica-
tions of arsenicosis including skin disorders and other features
such as weakness and muscles cramps, respiratory problems,
anemia, and gastrointestinal problems were observed among
the children of Dadu district. So, it is concluded that the
groundwater of Dadu district is not suitable for drinking and
cooking. However, it can be utilized for other domestic uses.
Thus, mitigation strategy needs to be location specific, de-
pending on the availability of As-safe options. Other alterna-
tive safe water options such as surface water, deep dug-wells,
Baig et al.
and rainwater harvesting may also be explored, with measures
against bacterial and other chemical contaminants.
Additionally, generating awareness about the As problem
and adequate supply of As-safe water to the affected popula-
tion is required. It is clear that urgent action is needed now to
prevent further children exposure to As in study area.
Acknowledgments The authors are grateful for the partial financial
support of the Nationalal Centre of Excellence in Analytical Chemistry
(NCEAC), Jamshoro and Young Welfare Society (YWS) Sindh, Pakistan.
The authors would like to thank to YWS Sindh, Pakistan for their help in
sampling with contection of local NGOs.
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