December 2010, Volume 1, No.

2
International Journal of Chemical and Environmental Engineering

Assessment of Groundwater Quality with Focus on

Arsenic Contents and Consequences. Case Study of
Tando Allahyar District in Sindh Province
S. A. Majidano1*, G. M. Arain1, D. R. Bajaj2, P. Iqbal2 and M. Y. Khuhawar1
1
. Institute of Advanced Research Studies in Chemical Sciences, University of Sindh, Jamshoro, Pakistan.
2
. Liaquat University of Medical and Health Sciences (LUMHS), Jamshoro, Pakistan.
*Corresponding Author Phone No. +9222-9213213 Fax No. +9222-9213213
E-mail:subhan_majidano@yahoo.com

Abstract
175 Groundwater samples collected across the district Tando Allahyar (TA) Sindh, Pakistan were analyzed for electrical conductivity
(EC), total dissolved salts (TDS), pH, cadmium (Cd), nickel (Ni), copper (Cu), iron (Fe), manganese (Mn) and arsenic (As) levels. The
arsenic presence varied from undetectable to 300 ppb, averaging overall 123 ppb. Sampling site S9 contained highest arsenic
concentration in the sampling area with a mean of 170 ppb. An apparent correlation between public health of the area and arsenic
levels in water seems to exist. Streaks of pigmentation were also observed randomly in some individuals. The concentrations of heavy
metals (Cd, Ni, Cu, Fe and Mn) varied in the ranges: 1-17, 12-95, 72-87, 14-1354 and 2-645ppb respectively. Only 9 of the total
samples taken adhered to water quality parameters set by WHO and Pakistan Standard Quality Control Authority for drinking water.

Key words: Arsenic levels in groundwater, Sindh, Pakistan.

1. Introduction
It is now fairly well established that Arsenic
happens to be the major contaminants in groundwater [1]
and a number of countries face arsenic contamination and
related health hazards [2-9] including its reported
carcinogenicity [9]
The main source of arsenic exposure is through
arsenic contaminated drinking water, food cooked in that
water and milk of the animals reared on arsenic
contaminated water. The long time use of arsenic
contaminated water may cause cancer [9, 10]. There are
no any known beneficial health effects from exposure to
arsenic.
The sources of arsenic in groundwater are
geochemical [1]. The arsenic is present in earth's crust
and sediment as the component of so many minerals, like,
ores containing sulfide along with copper, nickel, lead
and cobalt. Weathering of rocks converts arsenic sulfides
to arsenic trioxide which enters the arsenic cycle on
dissolution in groundwater [11, 12]. There are some point
sources of arsenic contamination like pesticides, fossil
fuel combustion, treated wood and smelting and mining
wastes [13].
Arain et al [14] earlier reported the arsenic contents
of groundwater of the districts Khairpur Mirs and Matiari;
in Sindh province and Nickson et al monitored the arsenic
contamination of groundwater of some districts of Punjab
province of Pakistan [15]. The present work reports the
quality and the arsenic, cadmium, nickel, copper, iron and
manganese contamination of groundwater of Tando
Allahyar (TA) district and its apparent effects on human
health.
2. Materials and Methods
The Arabian Sea is about 200 Km in its south-west.
The source of groundwater for human consumption, in the
area is a shallow aquifer created and recharged partially
by the scarce rainfall and mostly by permeation of water
from the unlined canal from mainstream River Indus that
runs in the periphery of sampling area. In the absence of
treated piped water the residents resort to groundwater for
drinking as well as supplementing canal water for
irrigation.
2.1 Sampling Area
The samples were collected from different towns
and villages of the district Tando Allahyar of Sindh
province. The district is located at longitudes 68051'16E to
68022'03E and latitudes 25017'33N to 25037’43N. The
map of the district along with sampling sites is given in
Figure 1.
2.2 Sample Collection
175 groundwater samples were collected from
across 22 sampling sites of district Tando Allahyar Fig 1.
The water samples collected were hand pumps 96,
electrical pumping motors 74, tube wells 04 and open
wells 01 at the depth of about 120, 150, 300 and 200 feet
respectively. The fresh water samples were collected after
 draining the pipe lines. The samples were collected in 1
L Teflon bottle rinsed with distilled water and sample.
Longitudes/latitudes were noted with GPS Magellan
Explorist 100, No. 0706, San Dimas CA 91773 USA, a
product of Thales Navigation China, at the sampling sites
and the Contour diagram was made with Golden
Software, Inc., Surfer, version 8.0.20.0 on the computer
(Fig. 2).
Figure.1 Map of district Tando Allahyar showing 22 samling
locations of heterogenous soil composition and (no of samples taken
from each location).
1.Tandho Allahyar Town (27), 2.Bukera Sharif Town (2), 3.Dhingano
Bozdar (2), 4. Kamaro Sharif (2), 5.Geo Kakepota (1), 6.Shaikh Moosa
(1), 7.Dito Kalro (1), 8.Sultan Khuwaja (1), 9.Allah Bux Arbab (27),
10.Khair M.Jarwar (10), 11.Misree Jarwar (17), 12.Saleh Halepoto (22),
13.Fazal M.Talpur (10), 14.Piaro Lund (23), 15.Wahyal Thebo (1),
16.Juman Lund (1), 17.Mal K.Thebo (1), 18.Tando Soomro (9),
19.Chamber Town (14), 20.KK Daidano (1), 21.GH Kapri (1), 22.MK
Khaskheli (1).
2.3 Sample Analysis
2.3.1 pH
pH was measured and adjusted to pH 2, with
ORION 420 A (Orion Research Inc. Boston USA) in the
laboratory.
2.3.2 EC and TDS
The EC and TDS were in situ measured with
conductivity meter ORION 115 (Orion Research Inc.
Boston USA) model.
2.3.3 Arsenic
Arsenic was determined by Merck Arsenic Kit
(0.01-0.5mg/L) (Merck K Ga A, 64271 Darmstadt,
Germany) in the laboratory within 48 hours of sampling.
The urine samples of eight volunteers (4 controlled and 4
random) were also tested for arsenic presence at the
sampling location.
As cross check the arsenic concentration of 26 water
samples was also measured on VARIAN Spectr AA-20
atomic absorption spectrophotometer connected with
Analytik Jena 1190121 hydride generator and quartz cell
6 cm. The signal was processed by Win AAS version 3.0
software interfaced with the instrument. The analysis was
carried out at integration mode having auto zero time 3.0
92
s and peak area 60 s and quartz cell temperature 9500C.
The absorbance was measured at 193.7 nm.
The analyte (sample 10ml + 1 ml HCl (37%);
alkaline borohydride (NaOH 10g + NaBH4 30g / L) was
placed in a sample cell and the resulting Arsenic swept
with argon (18L/hr). The analysis cycle continued with
pre wash time 20 s, pump time 7 s, reaction time 50 s and
rewash time 30 s. The average response for three replicate
measurements was quantized (5-30 ppb).
2.3.4 Cd, Ni, Cu, Fe and Mn
Sample 100 ml containing 1 ml conc. HNO3 was
concentrated to 10 ml by heating at 90-950C on water
bath. The heavy metals Cd, Ni, Cu, Fe and Mn were
analyzed by VARIAN Spectr AA-20 atomic absorption
spectrophotometer with air acetylene flame at the
conditions recommended by the manufacturer. The
analysis was carried out in triplicate (n = 3) with
integration time 3 sec and delay time 3 sec.
3. Results and Discussion
3.1 Location
The district Tando Allahyar with 22 (S1 to S22)
sampling sites and a number of samples taken from each
point is shown in Fig. 1. The district is located at
longitudes 68051'16E to 68022'03E and latitudes from
25017'33N to 25037’43N and the contour map of the
sample points and their Arsenic levels is drawn in Fig. 2.
3.2 pH
The pH of the water samples of the study area lay
between 6.63 and 8.15. pH at 16 sites was slightly acidic
(6.63-6.99); at one site neutral (7.00) and at rest of the
sites slightly basic (7.03-8.15).
3.3 Electrical Conductivity (EC) and Total Dissolved
Salts (TDS)
The electrical conductivity (EC) and total dissolved
salts (TDS) of the water samples of the study area
fluctuated in the range of 533-19450 µS/cm and 341-
12448 ppm respectively. Maximum value of EC and TDS
(19450 µS/cm and 12448 ppm respectively) was detected
in sample collected at S9 and the minimum value
observed in the sample taken at S13. The enormous
difference in EC and TDS at different sampling locations
may be due to the difference
Figuire. 2. Contour map of Arsenic contents of Tando Allahyar.
 in the geology of the groundwater of the sampling area. groundwater of these countries is rated as highly
The EC and TDS of only 22 (13% of the total samples) contaminated. Thus 26% samples within 50ppb may also
were within and all the remaining samples were above the be considered within permissible limits.
limits set by WHO (TDS 500 ppm). Based on the salinity The site S1 and its periphery was highly
index by Rabinove et al [16], the groundwater was non contaminated with arsenic, the arsenic contents of the
saline at 113 samples, slightly saline at 58 samples, groundwater samples of this part of the district fell
moderately saline at 02 locations and highly saline at 02 between below the limit of detection
samples (Table 1). Table.2 Arsenic concentration of water samples collected from sub-
district units (talukas) of district Tando Allahyar.
Table.1 Classification of water samples on the basis of total Name of Taluka Tando Jhando Chamber Total
dissolved salts. Allahyar Maree
Classification of Total dissolved salts No of samples No of Samples 122 36 17 175
groundwater (ppm) collected
Samples with As 32 22 13 67
Non saline < 1000 113 conc. below (LOQ)
Samples arsenic 89 14 4 107
Slightly saline 1000-3000 58 contaminated
Samples with As 55 23 14 92
Moderately saline 3000-10000 2 conc. within WHO
Very saline > 10000 2 limits (0-10ppb)
Samples with As 66 13 3 82
3.4 Arsenic conc. Above 10ppb
Samples with As 56 4 0 60
The arsenic contents of only 9 samples of these 22 conc. 100ppb or
samples were within 10ppb and one sample indicated above
25ppb. The samples with acceptable EC and TDS showed Samples with As 33 3 1 37
conc. 200ppb or
elevated levels of arsenic (except 9 samples) and those above
with low concentration of arsenic indicated higher values LOQ= limit of quantitation
of EC and TDS than the WHO recommendations. Thus (BDL) and 300ppb. Arsenic in 56 (46%) water
164 samples (94 %) were found unsuitable for drinking samples were 100ppb or above and that of 33 (27%) were
purpose. 200ppb or above. It is obvious that 46% population of the
Arsenic in water samples ranged between below the area drink water having arsenic up to 100ppb or above;
detection limit (BDL) and 300ppb; maximum arsenic causing a number of health hazards [2, 9].
(300ppb) was detected in 6 samples (Fig. 3). Continuous use of arsenic contaminated water over
A negative correlation of arsenic concentration with prolonged periods may cause cancer [9, 10]. Since arsenic
the EC and TDS of the water samples was recorded (r = - poisoning of human body takes place over prolonged
0.2687). Out of 175 groundwater samples analyzed, period, symptoms of arsenicosis [3] (a term now used for
arsenic concentrations of 67 (39%) samples were found arsenic related health disorders), are not well pronounced;
below the limit of quantitation (LOQ) and 107 (61%) an attempt was therefore made to correlate semi-empirical
samples were found arsenic contaminated parameters like pigmentation of human skin, retention of
arsenic by human body and its excretion through urine,
were monitored. Table 3 lists data on arsenic through
urine of eight subjects (4 controlled and 4 random) of site
S9. The selection criterion of person for study was based
on (i) their long term residence at areas having maximum
arsenic presence, (ii) having pigmentation effects and (iii)
constrained to use more of underground water than
surface or piped water. The data summarized in table 2
assumes a person to consume 3L/day of underground
water 250ppb of arsenic, his urine (1.5L/day) indicates
the presence of Arsenic averages between 100-250ppb,
this difference in volume between the water intake and
Figure.3 Arsenic concentration of water samples collected from
excretion leaves about 50% of arsenic in his blood stream
district Tando Allahyar
susceptible to accumulation in various organs. Controlled
(Table 2). The arsenic in 25 samples (14%) was volunteers were examined by a panel of dermatologists of
within the limits of WHO (10ppb) and that of 45 (26%)
Liaquat University of Medical and Health Sciences
samples was within 50ppb. The permissible limit for
(LUMHS) Jamshoro, Sindh, Palkistan. 15 of whom were
arsenic contamination in drinking water by India and
diagnosed for arsenicosis.
Bangladesh has been fixed to 50ppb because the

93
 Table. 3 EC, TDS, Salinity, pH and arsenic contents of water Table.4 Comparison of arsenic contents of water samples analyzed
samples consumed by the inhabitants and arsenic concentration of by kit method and atomic absorption.
their urine samples
S. As ppb As ppb As ppb As ppb
Gender EC Sal
S. No
S TDS pH As As No with Kit with AAs with Kit with AAs
No and µS/c ppm g/L water ppb ppb 1 50 38 14 5 2.0
Age m water water water urine
water
2 50 46 15 150 123
3 50 55 16 25 17.4
1 M17 1055 675 0.5 7.48 200 100 4 25 19 17 10 7.8
2 M15 1055 675 0.5 7.48 200 100 5 5 3.5 18 200 212
3 F45 1437 920 0.7 7.35 300 75 6 10 14.4 19 250 243
4 F30 1627 1041 0.8 7.20 300 75 7 250 228 20 100 109
5 F25 1451 929 0.7 7.45 250 75 8 25 21.5 21 0 0.42
6 F15 1422 910 0.7 7.64 250 150 9 5 3.9 22 150 139
7 F40 1011 647 0.5 7.24 250 75 10 150 170 23 250 235
8 F50 1232 788 0.6 7.38 250 100 11 150 163 24 50 34
12 150 137 25 250 190
The arsenic contents of water samples analyzed by 13 5 1.7 26 50 41
kit and atomic absorption spectrophotometer are
compared in (Table 4). No any significant difference was 3.6 Nickel (Ni)
observed between the arsenic contents of water samples Sources of nickel in water include contamination
analyzed by kit and atomic absorption spectrophotometer. from municipal sewage sludge, waste water from sewage
Gender based study showed that females tend to retain treatment plants and groundwater near landfill sites [19].
more Arsenic than males most probably because they The nickel concentration of the water samples of the
utilize the maximum amount of arsenic contaminated study area was found from 12 to 95ppb (Fig. 5). The
water as they spent most of their time within the area as normal threshold for nickel concentration prescribed by
compared to men. WHO is 1300ppb. All the samples were found within the
3.5 Cadmium (Cd) limits. A negative coefficient of correlation was observed
Cd is also toxic metal; it can impair kidney and between Ni and arsenic (r = -0.085). The most common
testicular tissue and may damage red blood cells [17-18] adverse effects of nickel are skin allergies and dermatitis.
and filtering mechanism. Cd is extremely toxic to aquatic The lung is the target organ for nickel toxicity in humans
biota even at low concentrations [18]. The WHO safe [19].
guideline of Cd in drinking water is 10ppb. Only 26 %
water samples of the study area indicated Cd contents
within the limits, while remaining 74 % samples indicated
above the limits. The contents of Cd in the water samples
of the study area ranged between 1ppb and 17ppb (Fig.
4). A smaller correlation was noted between Cd and
arsenic (r = 0.052).

Figure 5. Concentration of Ni in water samples

3.7 Copper (Cu)

Figure 4. Concentration of Cd in water samples
172 water samples (out of 175) indicated the
presence of copper. The copper contents varied between
below the limit of detection (BDL) and 87ppb (Fig. 6).
Thirteen samples were found as highly contaminated with
copper concentration of 52-87ppb. The WHO acceptable
limit of Cu is 30ppb. 74 % water samples indicated the
Cu contents within and 26 % samples above the limits.
The over doses of Cu may lead to neurological
complications, hypertension, liver and kidney dysfunction
[20-22]. Cu indicated lower correlation with arsenic (r =
0.053).

94

Figure 6. Concentration of Cu in water samples
3.8 Iron and Manganese (Fe and Mn)
Iron is an essential element with no any significant
health effect, but develops a yellowish color and a
peculiar taste when present in high concentration in water
bodies. Iron contents of the water samples varied in the
range of 14-1354ppb. 26 % of the water samples
indicated the concentration of iron 500ppb or above may
be due to geological reasons. In general, the water
samples of the study area contained higher contents of
iron, which indicates that the local mineral deposits in the
catchment’s area studied may have high levels of iron.
The WHO threshold for iron in drinking water is 300ppb.
Iron concentration of 44 % samples was observed above
and 56 % samples within the permissible limits [23]. As
the sources of arsenic in groundwater is weathering of the
arsenopyrite or other primary sulfide minerals [13] so the
groundwater of the study area contains higher levels of
arsenic as well as iron. The area is the old stream of the
Indus and Indus takes the sediments containing arsenic
from Himalayas. The arsenic present in these sediments is
sorbed onto the mineralogical hosts like hydrated ferric
oxide which acts as a sorbent or host for arsenic. There
fore the arsenic contaminated water also containing the
higher concentration of Fe.
Manganese concentration of the water of the study
area ranged between 2ppb and 645ppb. 53 % samples
showed within and 47 % samples above the limits of
(100ppb) of Mn set by WHO for drinking water [24]. The
sources of manganese are also minerals containing
manganese and dissolved when groundwater percolates
through the soil and rocks. Iron and manganese can affect
the flavor and the color of food and water; they may react
with the tannis in tea, coffee and some alcoholic
beverages to produce a black sludge, which will affect
both the taste and appearance. Iron and manganese
produce bacteria (iron manganese bacteria) which do not
pose a health threat; however, they do produce a red-
brown (iron) or black-brown (manganese) slime in toilet
tanks and can clog water system [25]. A higher
correlation between Mn and As (0.96) and Fe As (0.9)
was observed, which indicates the occurrence of these
elements from same type of origin or ores. It is also
reported that arsenic contaminated groundwater contained
levels of Mn and Fe above the prescribed values of WHO
[13].
95
4. Conclusion
Preliminary results on arsenic presence carried out
in a district of Sindh, Pakistan indicate higher levels of
the arsenic (up to 300ppb) than the recommended world
and national standards. The trends in this report support
similar and earlier findings of the present researchers for
other districts of Sindh within a radius of about 200 Km
of the present study area. In India and Bangladesh it is
already well established that certain areas of both the
countries show elevated levels of Arsenic. Now Pakistan
seems to join their ranks. It is pertinent therefore that soil
composition, pesticide and organic fertilizer use be
closely monitored for toxic metals specifically arsenic.
REFERENCES
[1] G. J. Alaerts and N. Khouri, “Arsenic contamination of groundwater:
Mitigation strategies and policies”, Hydrogeol. Jour., vol. 12, pp.
103-114, 2004.
[2] D. N. G. Mazumder, R. Haque, N. Ghosh, B. K. De, A. Santra, D.
Chakaraborty, A.H. Smith, “Arsenic in drinking water and the
prevalence of respiratory effects in West Bengal, India”, Int. Jour.
Epidemiol., vol. 29, pp. 1047-1052, 2000.
[3] T. Agusa, T., Kunito, J. Fujihara, R. Kubota, T. B. Minh, P. T. K.
Trang, H. Iwata, A. Subramanian, P. H. Veit, S. Tanabe,
“Contamination by arsenic and other trace elements in tube-well
water and its risk assessment to humans in Hanoi, Vietnam”,
Environ. Pollut., vol. 139, pp. 95-106, 2006.
[4] D. Maddison, R. Catala-Luque and D. Pearce, “Valuing the arsenic
contamination of groundwater in Bangladesh”, Environ. & Resour.
Econo., vol. 31, pp. 459-476, 2005.
[5] K. Ohno, T. Yanase, Y. Matsuo, T. Kimura, M. H. Rahman, Y.
Magara and Y. Matsui, “Arsenic intake via water and food by a
population living in an arsenic affected area of Bangladesh”, Sci.
of the Total Environ., vol. 381, pp. 68-76, 2007.
[6] D. Dass, G. Samanta, B. K. Mandhal, T. R. Chowdhury, C. R.
Chanda, P. P. Chowdhury, G. K. Basu and D. Chakraborti,
“Arsenic in groundwater in six districts of West Bengal, India”,
Environ. Geochem. and Heal., vol. 18, pp. 5-15, 1996.
[7] J. K. Gurung, H. Ishiga, M. S. Khadka, “Geological and geochemical
examination of arsenic contamination in groundwater in the
Holocene Terai Basin”, Nepal, Environ. Geol., vol. 49, pp. 98-113,
2005.
[8] T. Yoshida, H. Yamauchi and G. F. Sun, “Chronic health effects in
people exposed to arsenic via the drinking water: dose-response
relationships in review”, Toxicolo. And Appl. Pharmacol., vol.
198, pp. 243-252, 2004.
[9] D. Q. Hung, O. Nekrassova and R. G. Compton, “Analytical
methods for inorganic arsenic in water: a review”, Talanta, vol. 64,
pp. 269-277, 2004.
[10] P. K. Dasgupta, H. Huang, G. Zhang and G. P. Cobb, “Photometric
measurement of trace As(III) and As(V) in drinking water”,
Talanta, vol. 58, vol. 153-164, 2002.
[11] B. K. Mandhal and K. T. Suzuki, “Arsenic round the world: a
review”, Talanta, vol. 58, pp. 201-235, 2002.
[12] F. Shemirani, M. Baghdadi and M. Ramezani, “Preconcentration
and determination of ultra trace amounts of arsenic (III) and
arsenic (V) in tap water and total arsenic in biological samples
 by cloud point extraction and electrothermal atomic absorption [20] S. S. Gowd, P. K. Govil, “Distribution of heavy metals in surface
spectrometry”, Talanta, 65, pp. 882-887, 2005. water of Ranipet industrial area in Tamil Nadu, India”, Environ.
Monit. Asses., vol. 136, pp. 197-207, 2008.
[13] S. Ahuja, “Arsenic contamination of groundwater, mechanism,
analysis and remediation”, John Willey & Sons, Inc.
[21] M. S. Rao, R. Gopalkrishnan and B. R. Venkatesh, Medical
Publication, Hoboken, New Jersey, USA, pp 7-31, 2008.
geology- An emerging field in environmental Science. National
Symposium on Role of Earth Sciences. Integrated and Related
[14] G. M. Arain, M. Aslam, S. A. Majidano and M. Y. Khuhawar, “A
Societal issue. GSI Spl. Pub. No. 65 (II), 213 (2001).
preliminary study on arsenic contamination of Matiari and
Khairpur Mir's districts of Sindh, Pakistan”, J. Chem. Soc. Pak.,
[22] A. K. De, “Environmental Chemistry”, Eiley Eastern Ltd., New
vol. 29, pp. 463-467, 2007.
Delhi, 157 (1987).
[15] R. T. Nickson, T. M. McArthur, B. Shrestha, T. O. Kyaw-Myint, D.
[23] J. Y. Lee, J. C. Choi, M. J. Yi, J. W. Kim, J. Y. Cheon, Y. K. Choi,
Lowry, “Arsenic and other drinking water quality issues,
M. J. Choi and K. K. Lee, “Potential groundwater
Muzaffargarh District, Pakistan”, Appl. Geochem., vol. 20, pp. 55-
contamination with toxic metals in and around an abandoned Zn
68, 2005.
mine, Korea”, Water, Air, and Soil Pollution, vol. 165, pp. 167-
185, 2005.
[16] C. L. Rabinove, R. H. Longford, J. W. Brookhart, US Geog., Sur.
Water Supply Paper 1958, 1812, 72.
[24] A. Wilson, K. Parrott and B. Ross, Iron, Virgion Cooperative
[17] J. H. Duffus, “Environmental Toxicology”, Resource and
Extension, USA, Publication No. 356-478 (1999).
Environmental Science Series, Wdward Arnold (Publisher) Ltd.,
London, 75 (1980).
25] S. K. Alvi, F. A. Khan, I. Siddiqui, U. Aasghar and T. H. Usmani,
“Trace metals contamination in groundwater of SITE area,
[18] M. Akif, A. R. Khan, K. Sok, K. S. Min, Z. Hussain, Maal-Abrar,
Karachi”, J. Chem. Soc. Pak., vol. 28, pp. 223-230 2006
M. Khan and A. Muhammad, “Textile effluents and their
contribution towards aquatic pollution in the Kabul
River (Pakistan)”, J. Chem. Soc. Pak., vol. 24, pp. 106-111,
2002.

[19] A. L. L. Larocque and P. E. Rasmussen, “An overview of trace

metals in the environment, from mobilization to remediation”,
Environmental Geology, vol. 33, pp. 85-91, 1998.

96