Environmental Geochemistry of Surface and Subsurface Water from Dera Ismail Khan Division, Khyber Pakhtunkhwa, Pakistan

Abstract

The Dera Ismail Khan division is situated in the southern most part of the Khyber-
Pakhtunkhwa province in Pakistan. Majority of population in this region obtain domestic water from
tube wells, dug wells, ponds, stored run off of the Indus and Gomal rivers and perennial streams.
This study is aimed to determine the physio-chemical contaminants in the surface and subsurface
water which could cause environmental problem. For this purpose, representative water sample were
collected from tube wells, dug wells, streams and rivers. These analyses were performed using Hach
DR/2000 spectrophotometer and graphite furnace atomic absorption spectrometer. Chemically both
surface and subsurface water samples of the area were classified as alkaline fresh water. The
comparison of the data with standard limits set by Word Health Organization (WHO) for drinking
water suggested that in certain areas of the division, the drinking water samples have high
concentrations of Total Dissolved Solids, NO3
2-, SO4
2-, F-, Cl-, Fe2+, Ca2+, Mg2+, Pb2+, Ni2+ and Cd2+
while pH, EC, HCO3
-, PO4
3-, Na+, Mn2+, K+, Cr3+ and Zn2+ were within the permissible limits. These
contaminations could be attributed to the geogenic sources which might be responsible for the health
related problems in certain areas of the division.

Full text

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 243
Environmental Geochemistry of Surface and Subsurface Water from
Dera Ismail Khan Division, Khyber Pakhtunkhwa, Pakistan
1MOHAMMAD TAHIR SHAH*, 2ANWAR HUSSAIN ALIZAI AND 3SHUHAB DANISHWAR KHAN
1NCE in Geology, University of Peshawar, Peshawar, Pakistan.
2Geological Survey of Pakistan, Pakistan.
3Department of Earth and Atmospheric Sciences, University of Houston, Houston, USA.
tahir_shah56@yahoo.com*
(Received on 30th September 2010, accepted in revised form 22nd September 2011)
Summary: The Dera Ismail Khan division is situated in the southern most part of the Khyber-
Pakhtunkhwa province in Pakistan. Majority of population in this region obtain domestic water from
tube wells, dug wells, ponds, stored run off of the Indus and Gomal rivers and perennial streams.
This study is aimed to determine the physio-chemical contaminants in the surface and subsurface
water which could cause environmental problem. For this purpose, representative water sample were
collected from tube wells, dug wells, streams and rivers. These analyses were performed using Hach
DR/2000 spectrophotometer and graphite furnace atomic absorption spectrometer. Chemically both
surface and subsurface water samples of the area were classified as alkaline fresh water. The
comparison of the data with standard limits set by Word Health Organization (WHO) for drinking
water suggested that in certain areas of the division, the drinking water samples have high
concentrations of Total Dissolved Solids, NO32-, SO42-, F-, Cl-, Fe2+, Ca2+, Mg2+, Pb2+, Ni2+ and Cd2+
while pH, EC, HCO3-, PO43-, Na+, Mn2+, K+, Cr3+ and Zn2+ were within the permissible limits. These
contaminations could be attributed to the geogenic sources which might be responsible for the health
related problems in certain areas of the division.
Introduction
Water quality can be evaluated by physical,
chemical and biological parameters. It can be highly
affected by wide range of geogenic and
anthropogenic sources which indicates a complex
variation over different spatial and temporal scales
[1-3]. All over the populated part of the earth, the
quality of natural fresh water is being disturbed by
human activities. This is mainly due to the discharge
of the municipal and industrial waste into the rivers.
However, the addition of soluble matters from the
catchment areas and from fertilizer of crop fields also
play a role in contaminating the rivers and hence
cause pollution in underground aquifers [4]. The
excess of anions, cations and heavy and trace metals
in the water because of their toxicity, especially in
drinking water, may cause serious environmental
health problems such as raising blood pressure,
chronic anemia, stomach ramps, nausea, skin
irritation, methemoglobinemia and carinogenisis etc.
[4-6]. Water pollution in Pakistan, like other
underdeveloped countries, is a widespread
environmental problem which needs to be properly
monitored. The water quality of Dera Ismail (D. I)
Khan division has, therefore, been investigated
during present study.
The Dera Ismail (D.I.) Khan division is
situated in the southern-most part of the Khyber-
Pakhtunkhwa (KP) province between latitude 31o 15΄
and 32o 30΄ N and longitude 70o 00΄ and 71o 25΄ E
(Fig. 1). It contains two main physiographic units, 1)
the alluvial lowlands, which include the structurally
undisturbed Indus plains, and 2) the folded belt,
which includes the Khisor, Murwat, Bhittanni, and
Sulaiman ranges. These ranges and highlands form a
nearly continuous mountain system between Salt
Range and Potwar Plateau extending to the
Balochistan province in the southwest. The climate of
the region is sub-arid to subtropical continental
lowland type. The average annual precipitation
ranges from 290 mm in the hills in the north to 200
mm in Ramak in the south. More than 80%
population of the D.I. Khan division is living in rural
areas. These people obtain their domestic water from
dug-wells and shallow drilled wells equipped with
hand-pumps, ponds, stored runoff, the Indus and
Gomal rivers and perennial streams. The public
Health Engineering Department (PHED) drilled tube-
wells for the supply of drinking water in major
towns. Indus River forms the eastern boundary of the
D.I. Khan division while the Gomal River flows
through most parts of the division. The total surface
covered by vegetation rarely exceeds ten percent as
compared to the whole land [7].
J.Chem.Soc.Pak., Vol. 34, No. 1, 2012
*To whom all correspondence should be addressed.

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 244
Fig. 1: Map of D. I. Khan division showing various localities and samples locations.
Several field surveys in this region revealed
that numerous people complained about the
increasing numbers of abdominal and skin diseases
which are usually caused by the bacteriological and
chemical contaminants in drinking water. The
scarcity of drinking water in the region and the use of
domestic water from different sources and the
increasing trend of various diseases have made the
basis for investigating the quality of water of the
division. This study was, therefore, designed to
determine the physio-chemical characteristics of
surface and subsurface water in regard to their
environmental impact in the area.
Results and Discussions
Average physio-chemical parameters of
triplicate drinking water samples of both surface and
subsurface water of the D.I. Khan division were
statistically evaluated and the results are given in the
Table-1. The surface water included samples
collected from the streams and rivers while the
subsurface water was divided into shallow water (<30
m) and deep water (>100 m). Deep water included
water from tube wells and the shallow water included
water from dug wells and springs.
The water samples were plotted in the Piper
[8] diagram (Fig. 2). Majority of surface and
subsurface water samples were plotted within the
field of Na+-K+, Cl--SO4
2- type (normally called as
alkaline earth fresh water) while some were plotted in
the HCO3
-, Ca2+-Mg2+ type and Ca2+-Mg2+, HCO3
-
type (Fig. 2). This classification scheme suggests that
the water from various sources in the D.I. Khan
division is generally alkaline fresh water.
Physical Parameters
pH
pH in most of the samples was found less
than 7.00, but in some samples collected from the
northern part showed high pH. The highest pH value
(9.07) was found in a dug well sample obtained from
Gul Imam village while the lowest value (6.91) was
found in the tube well sample of D.I. Khan colony. It
was also observed that the pH in deep water was
relatively lower than the surface and shallow water.

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 245
Table-1: Statistical summary of the water samples from D. I. Khan division.
Parameters Surface water samples (N = 9) Shallow water samples (N = 7) Deep water Samples (N = 17) WHO
(Rivers and streams) (Dug wells and springs) (Tube wells) limits
Unit Min Max Mean SD Min Max Mean SD Min Max Mean SD
T °C 19.5 33.2 24.7 4.8 22.8 27.9 25.3 2.3 21.3 33.4 25.4 3.5 --
pH -- 7.8 8.5 8.1 0.3 7.5 9.1 8.0 0.6 6.9 8.2 7.6 0.3 6.5-8.5
EC µS/cm 310 1130 612 344 460 1600 976 365 500 3000 1246 697 --
TDS mg/L 217 791 429 241 322 1120 683 255 350 2100 885 489 <1000
HCO3- mg/L 75.0 362.5 166.9 98.1 125.0 445.0 264.3 108.6 125.0 460.0 225.6 97.3 --
NO3- mg/L 0.4 2.6 1.1 0.7 0.1 90.0 16.9 32.8 0.1 3.2 1.0 1.0 50
SO4-2 mg/L 15.0 400.0 135.6 146.5 55.0 425.0 201.4 149.9 50.0 1600.0 447.9 398.4 250
PO4-2 mg/L 0.04 0.19 0.11 0.06 0.08 0.29 0.13 0.07 0.02 0.60 0.09 0.14 --
Cl mg/L 24.4 269.1 97.8 93.4 40.0 333.0 173.4 121.6 45.0 618.0 191.9 142.5 250
F mg/L 0.1 0.7 0.4 0.2 0.9 4.6 2.2 1.3 0.1 1.8 0.7 0.5 1.5
Ca+2 mg/L 22.5 51.7 34.5 9.6 6.4 68.1 39.6 20.9 7.7 85.5 53.0 22.3 --
Mg+2 mg/L 11.8 47.0 19.6 13.0 9.0 49.2 30.5 15.5 0.5 89.3 38.9 27.0 --
Fe+2 mg/L 0.3 43.3 9.9 15.2 0.6 5.8 2.2 2.0 0.1 12.7 2.5 3.2 0.3
Mn+2 mg/L 0.05 0.80 0.16 0.28 0.01 0.11 0.05 0.04 0.02 0.51 0.14 0.13 0.50
Na+ mg/L 15.2 179.5 62.2 62.3 27.1 214.0 110.0 75.0 21.9 402.5 116.2 94.8 200
K+ mg/L 3.4 9.5 4.8 2.2 1.7 11.4 5.8 3.5 2.5 33.9 8.6 7.4 --
Cu µg/L 7.0 1000.0 140.9 375.0 6.0 26.0 11.3 7.1 <0.05 287.0 42.4 70.2 2000
Pb µg/L <0.05 287.0 44.3 106.5 1.0 13.0 5.6 5.1 <0.05 30.0 3.3 7.9 10
Zn µg/L <0.05 20.0 9.0 7.9 10.0 370.0 117.1 129.3 <0.05 50.0 20.6 14.8 3000
Cr µg/L <0.05 19.0 4.5 6.9 <0.05 16.0 2.9 5.9 <0.05 6.0 1.4 1.9 50
Ni µg/L <0.05 60.0 10.7 23.4 <0.05 <0.05 0.1 <0.05 <0.05 51.0 3.9 12.4 20
Cd µg/L <0.05 16.0 2.4 6.0 <0.05 12.0 2.8 4.8 <0.05 2.0 0.2 0.5 3
Fig. 2: Piper diagram [5] for the surface and
subsurface water of the D. I. Khan division.
Various fields are as: 1 = Na+-K+, Cl--SO4
2-;
2 = HCO3
-, Ca2+-Mg2+; 3 = Cl--SO4
2-, Na+-
K+; 4 = Ca2+-Mg2+, HCO3
-; 5 = Ca2+-Mg2+; 6
= Cl--SO4
2-; 7 = Na+-K+; 8 = HCO3
--CO3; 9
= SO4
2-; 10= Cl-; 11 = No dominant ;
HCO3
-; 13 = Mg2+; 14 = Na+/K+; 15 = No
dominant; 16 = Ca2+.
Electrical Conductivity (EC)
EC was found in the range of 310-1130
µS/cm, 460-1600 µS/cm and 500-3000 µS/cm in
surface, shallow and deep water respectively (Table-
1). The highest value (3000 µS/cm) of EC was found
in the water sample collected from a tube well in
Ramak area. However, EC in the surface water was
generally low.
Total Dissolved Solid (TDS)
TDS was found in the range of 217-791
mg/L, 322-1120 mg/L and 350-2100 mg/L in surface,
shallow and deep water samples respectively (Table
1). The deep water samples collected from tube wells
at Tank, Hathala, Potah, Poroa and Ramak and
shallow water sample collected from dug well at
Mullazai exceeded the permissible limit (1000 mg/L )
of WHO [9].
Anions
HCO3
-
The concentrations of bicarbonate were in
the range of 75.0-362.5 mg/L, 125.0-445.0 mg/L and
125.0-460.0 mg/L in surface, shallow and deep water
samples respectively (Table-1). The highest
concentration (460.0 mg/L) of HCO3
-
was found in
the tube well water at Chudhwan and the lowest
concentration (75.0 mg/L) was found in the water
sample collected from Indus River at Darya Khan.
NO3
-
The concentration of nitrate in D.I. Khan
area ranged from 0.4 to 2.6 mg/L, 0.2 to 90 mg/L
and <0.10 to 3.2 mg/L in surface, shallow and deep
water samples respectively (Table-1). Almost all the
samples of water of D. I. Khan area, accept one
sample of spring in Chadhwan, were having NO3
2-
within the permissible limit (<50 mg/L) of WHO [9].
The spring water at Chadhwan was, therefore, found
unsafe for health.

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 246
SO4
-
The sulphate contents in D I. Khan area
were found in the range of 15-400 mg/L, 55-425
mg/L and 50-1600 mg/L in surface, shallow and deep
water samples respectively (Table-1). The SO4
2-
contents of majority of the waters samples of surface
and shallow water and some of the deep water are
within the permissible limit (<250 mg/L) of WHO
[9]. However, the SO4
2- contents of water samples
collected from Gomal River (400 mg/L), stream at
Tank Zam (300 mg/L), dug well at Mullazai (375
mg/L) and spring at Chadhwan (425 mg/L) and tube
wells at Tank (450 mg/L), Umer Ada (450 mg/L),
Kullachi (700 mg/L), Hathala (775 mg/L) Potah (900
mg/L), D.I. Khan colony (275 mg/L), Daraban (450
mg/L), Chadhwan (450 mg/L), Poroa (1600 mg/L)
and Ramak (675 mg/L) exceeded the permissible
limit (<250 mg/L) of WHO [9]. Therefore, the
drinking water of these areas, especially from tube
wells, was found unsafe for health.
PO4
3-
Phosphate contents generally varied from
0.04 to 0.17 mg/L, 0.08 to 0.29 mg/L and 0.02 to
0.13 mg/L in surface, shallow and deep water
samples respectively (Table-1). All the water samples
of D. I. Khan were, however, found safe as far as the
PO4
3- concentration is concerned.
Cl-
Chloride concentrations ranged from 26 to
269 mg/L, 40 to 333 mg/L and 45 to 618 mg/L in
surface, shallow and deep water samples respectively
(Table-1). Chloride contents in the deep water at
Kullachi (293 mg/L), Hathala (333 mg/L), Potah (314
mg/L) and Ramak (618 mg/L), shallow water at
Mullazai (333 mg/L) and Yarik (312 mg/L) and
stream water at panyala (269 mg/L) exceeded the
permissible limit (<250 mg/L) of WHO [9].
However, Cl- contents in both Indus and Gomal
rivers were found low (<159 mg/L).
F-
Fluoride concentrations ranged from 0.12 to
0.67 mg/L, 0.89 to 4.57 mg/L and 0.10 to 1.79 mg/L
(Table-1). Fluoride contents at many places exceeded
the permissible limit (<1.5 mg/L) of WHO [9]. These
included the samples collected from shallow water at
Pezu (4.57 mg/L), Mullazai (2.54 mg/L), Gul Imam
(1.79 mg/L) and Yarik (2.72 mg/L) and deep water at
Mullazai (1.62), Panyala (1.52 mg/L) and Ramak
(1.79 mg/L). Rest of the samples of shallow and deep
water and almost all the surface water samples were
having F- contents below the permissible limit.
Major Cations
Ca2+
Calcium contents ranged from 22.5 to 51.7
mg/L, 6.4 to 68.1 mg/L and 7.7 to 85.5 mg/L in
surface, shallow and deep water samples respectively
(Table-1). As WHO [9] did not define the permissible
limit for Ca2+ in drinking water, therefore,
comparison with the permissible limit was not made.
However, relatively high amount (>80 mg/L) was
found in the deep water samples collected at Potah,
Daraban, Poroa and Ramak.
Mg2+
Magnesium concentration ranged from 11.8
to 47.0 mg/L, 9.0 to 49.2 mg/L and 0.51 to 89.3mg/L
in surface, shallow and deep water samples
respectively (Table-1). It exceeded the permissible
limit (<50 mg/L) of WHO [9] in the deep water
samples at Hathala (60.7 mg/L), Potah (89.3 mg/L),
Chadhwan (51.7 mg/L), Poroa (73.7 mg/L) and
Ramak (72.3 mg/L). However, all the surface and
shallow water samples showed Mg2+ concentration
below the permissible limit.
Na+
Sodium concentrations ranged from 15.2 to
179.5 mg/L, 43.7 to 188.5 mg/L and 30.3 to 402.5
mg/L in surface, shallow and deep water samples
respectively (Table-1). Only one water sample,
collected from Indus River at Chashma, exceeded the
permissible limit (<200 mg/L) of WHO [9] while rest
of the water samples were found below the
permissible limit.
K+
Potassium concentrations were found in the
range of 3.44-9.5 mg/L, 1.65-7.4 mg/L and 2.45-33.9
mg/L in surface, shallow and deep water samples
respectively (Table-1). Its concentration was
generally found <12 mg/L in all types of deep,
shallow and surface waters (Table-1). However, one
sample collected from tube-well at Panyala showed
relatively highest (33.9 mg/L) concentration of K+.
Fe2+
Iron ranged from 0.3 to 43.3 mg/L, 0.6 to
5.8 mg/L and 0.1 to 12.7 mg/L in surface, shallow

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 247
and deep water samples respectively (Table-1). It was
found lowest at Mullazai (0.1mg/L) and highest at
Gomal river (12.7 mg/L). Iron exceeded the
permissible limit (0.3 mg/L) of WHO [9] for drinking
water in almost all the water samples.
Mn2+
Manganese contents were found in the range
of 0.05-0.80 mg/L, 0.01-0.11 mg/L and 0.02-0.51
mg/L in surface, shallow and deep water samples
respectively (Table-1). In all the water samples Mn2+
concentration was found within the permissible limit
(<0.5 mg/L) of WHO [9].
Heavy and Trace Metals
Cu2+
Copper concentrations ranged from 7.0 to
1000.0 µg/L, 6.0 to 26.0 µg/L and <0.05 to 287.0
µg/L in surface, shallow and deep water samples
respectively (Table-1). All the water samples were
having Cu2+ within the permissible limits (<2000
µg/L) of WHO [9]. However, the Cu2+ concentration
in the water sample of Gomal River was relatively
high (1000 µg/L).
Pb2+
Lead concentrations were found in the range
of <0.05-287.0 µg/L, 1-13.0 µg/L and <0.05 to 16.0
µg/L in surface, shallow and deep water samples
respectively (Table-1). It was noted that the Pb2+
concentration in most of the surface water and two of
the deep water samples at Mullazai and Paharpur
exceeded the permissible limit (<10 µg/L) of WHO
[9]. However, the water sample from Indus River at
Darya Khan showed alarming concentration (287.0
µg/L) of Pb2+.
Zn2+
Zinc concentrations were found in the range
of <0.05-20.0 µg/L, 10.0 to 370.0 µg/L and <0.05 to
16.0 µg/L in surface, shallow and deep water samples
respectively (Table-1). Zn2+ contents in all the water
samples of D. I. Khan division were found within the
permissible limit (<300 µg/L) of WHO [9].
Cr3+
Chromium concentrations generally varied
from <0.05 to 19.0 µg/L , <0.05 to 16.0 µg/L and
<0.05 to 6.0 µg/L in surface, shallow and deep water
samples respectively (Table-1). All the water samples
showed Cr3+ within the permissible limit (<50 µg/L)
of WHO [9]. Relatively high Cr3+ contents, but
within the permissible limits, were noticed in the
water samples collected from Gomal River and
shallow water at Yarik.
Ni2+
Nickel concentrations in most of the water
samples of D.I. Khan were found below the detection
limit (<0.05 µg/L) (Table 3.1). However, deep water
at Hathala (51.0 µg/L), stream water at Pushapull
(60.0 µg/L) and Indus river water at Cheshma (32.0
µg/L) were exceeded the permissible limit (<20
µg/L) of WHO [9].
Cd2+
Cadmium concentrations were found in the
range of <0.05-16.0 µg/L, <0.05-2.0 µg/L and <0.0-
12.0 µg/L in surface, shallow and deep water samples
respectively (Table 1). Cadmium in the deep water
was found within the permissible limit (<3 µg/L) of
WHO [9]. It exceeded the permissible limit in
shallow water at Pezu (12.0 µg/L) and spring water at
Chadhwan (7.0 µg/L) and in the water of Indus River
at Chashma (16.0 µg/L).
The average contents of the selected anions,
cations and heavy and trace metals in surface and
sub-surface (shallow and deep) water were compared
with the permissible limits of WHO [9] in Fig. 3. It
was found that SO4
2- in deep water and F- in shallow
water exceeded the permissible limit of WHO [9]
while the SO4
2- and Cl- showed relatively high
concentration in deep water. The NO3
2- and F-,
however, showed relatively high concentration in
shallow water (Fig. 3). Among the cations, the
average Fe showed many fold high amount in all
types of water samples. The Mn2+ and Na+ showed
low concentration as compared the permissible limit
of WHO [9]. The average concentration of Pb2+
exceeded the permissible limit of WHO [9] while rest
of the heavy and trace metals showed lower amount
as compared to the WHO limits. Cu2+, Pb2+, Cr3+ and
Ni2+ showed relatively high concentration in surface

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 248
water while Zn2+ and Cd2+ showed relatively high
concentration in shallow water (Fig. 3).
The statistical correlation among the physio-
chemical parameters was performed by the statistical
software (SPSS) and the results are given in Table-2.
No significant correlation among most of the
parameters was observed in the water of D.I. Khan
division. However, some of the parameters having
correlation coefficients with p<0.05 were: pH-EC (r
= 0.997), pH-SO4
2- (r = 0.748), pH-Cl- (r = 0.886),
pH-Ca2+ (r = 0.711), pH-Mg2+ (r = 0.784), pH-Na+
(0.859), EC-SO4
2+ (r = 0.742), EC-Cl- (r = 0.878),
EC-Ca2+ (0.707), EC-Mg2+ (r = 0.791), EC-Na+ (r =
0.853), SO4
2+-Cl- (r = 0.516), Ca2+-SO4
2- (r = 0.690),
Mg2+-SO4
2- (r = 717), Na+-SO4
2- (r = 0.474), Na+-Cl-
(r = 0.937), Ca2+-Mg2+ (0.744), Mg2+-Na+ (r = 0.609),
Fe2+-Cu2+ (r = 0.926), Fe2+-Cr3+ (r = 0.782) and Cu2+-
Cr3+ (r = 0.795). These correlations suggested that the
heavy and trace metals behaved independently of
physical parameters, anions and major cations in the
water of D.I. Khan division while some of the major
cations, anions and physical parameters were found
interrelated. This could be due to the common source
(i.e., halite and gypsum etc.) or similar geochemical
behavior.
In the D.I. Khan division, the population is
generally restricted to the main towns such as D.I.
Khan and Tank and their premises. In most areas of
these towns, the inhabitants are using tube well water
for drinking and domestic purposes. In other areas of
the D.I. Khan division the population is extremely
scattered and is living in small densities in villages
where the tube wells water has been provided to very
limited areas. Most of the population living in these
villages is generally using the water of Indus and
Gomal rivers and their tributaries, streams, ponds and
dug wells for drinking and domestic purposes.
During this study water from all sorts of sources and
places was studied qualitatively. It was found that the
water of D.I. Khan division in certain areas may have
health risk, as the concentrations of some of the
chemical constituents are high. These areas are Tank,
Hathala, Potah, Poroa and Ramak, Pezu, Tank Zam,
Mullazai, Chadhwan, Umer Ada, Kullachi, D.I. Khan
colony, Daraban and Chadhwan. It was noticed that
among the various parameters such as TDS, NO3
2-,
SO4
2-, F-, Cl-, Fe2+, Pb2+, Ni2+ and Cd2+, not all but
one or more parameters, were found exceeding the
permissible limit of WHO [9] in the water samples of
these areas. However, SO4
2- and Fe2+ were found
above the permissible limit in the water samples of
many areas. Fluoride in few samples of shallow and
deep water exceeded the permissible limit while the
surface water has normal concentration of fluoride.
Pb2+ and Ni2+ were found above the permissible limit
in few samples of the surface water, however, very
high concentration (287 µg/L) in the water of Indus
River at Darya Khan and Ni2+ concentration (60
µg/L) in Pusha Pull was observed. These anomalies
could be localized and need to be further
investigated. The various types of diseases related
with the toxicity of these elevated anions and heavy
and trace metals may have drastic health effects on
the inhabitants of the area if used for longer duration
of time. Absence of major industries in the region
support that the sources of contamination in the water
of D.I. Khan may be geogenic and not the
anthropogenic, however, this could be a localized
phenomenon.
Table-2: Linear correlation matrix for physic-chemical parameters in the water of D. I. Khan Division (N =
33)
pH EC TDS HCO3 NO3 SO4 PO4 Cl Ca Mg Na K Fe Mn Cu Pb Zn Cr Ni Cd
pH 1 .997 -.352 0.246 -0.028 .748 -0.156 .886 .711 .784 .859 0.092 0.036 0.142 0.045 -0.269 0.013 -0.01 -0.076 -0.306
EC 1 -.380 0.266 -0.032 .742 -0.168 .878 .707 .791 .853 0.103 0.028 0.137 0.039 -0.272 0.011 -0.019 -0.081 -0.308
TDS 1 -0.282 0.011 -.369 0.13 -0.049 -.634 -.453 -0.053 -0.061 .339 0.06 0 .318 0.132 -0.092 .391 0.063 0.26
HCO3 1 .421 0.26 -0.048 0.088 0.331 .432 0.11 -0.129 -0.081 -0.259 0.001 -0.31 0.261 -0.094 -0.24 -0.053
NO3 1 0.051 0.024 -0.077 0.05 0.059 -0.055 -0.131 -0.04 -0.111 -0.069 -0.054 0.085 -0.072 -0.075 0.253
SO4 1 -0.261 .516 .690 .717 .474 0.027 0.017 0.018 0.054 -0.189 -0.098 -0.1 -0.016 -0.202
PO4 1 0.004 -0.231 -0.143 0.045 -0.028 -0.09 -0.079 -0.055 0.126 0.245 -0.111 -0.02 -0.104
Cl 1 .339 .508 .937 0.13 -0.033 0.19 -0.004 -0.224 0.005 0.036 -0.075 -0 .326
Ca 1 .744 .386 -0.057 0.122 0.073 0.077 -0.26 0.121 -0.103 -0.088 -0.158
Mg 1 .609 0.048 0.116 -0.183 0.162 -0.219 0.015 0.021 -0.024 -0.173
Na 1 0.179 0.001 0.044 0.009 -0 .21 0.026 0.053 -0.056 -0.292
K 1 -0.103 -0.136 -0.065 -0.09 -0.009 -0.106 -0.038 -0.116
Fe 1 0.261 .926 -0.078 -0.186 .782 0.102 0.061
Mn 1 0.157 -0.079 -0.198 0.232 -0.136 -0.183
Cu 1 -0.041 -0 .135 .795 0.005 0.013
Pb 1 -0.049 -0.021 -0.018 0.117
Zn 1 -0.189 -0.104 -0.04
Cr 1 0.01 -0.005
Ni 1 0.188
Cd 1
Bold correlation is significant at the 0.05 level (2-tailed)
Italic correlation is significant at the 0.01 level (2-tailed)

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 249
Fig. 3: Comparison of the average contents of
selected chemical parameters of surface and
subsurface water and WHO limit.
Experimental
Samples Collection and Preparation
Two sets of triplicate drinking water
samples were collected from different sources such as
tube wells, dug wells, springs, streams and rivers in
preconditioned polyethylene bottles in the densely
populated areas of D.I. Khan division (Fig. 1).
Precautionary measures were taken to avoid any
possible contamination during sampling. The newly
purchased unused polyethylene bottles were cleaned
with the ultrapure distilled water collected from the
Elga Purelab water purification plant. During
collection of each water sample, the bottle was again
washed with the same water and every possible care
was taken to avoid contamination during collection
and transportation of the sample. One set of samples
was collected in 500 ml bottles and were filtered
through 0.45 µm filter paper. The filtrates were
immediately acidified with 0.1 N HNO3 [10] and
stored at 4 °C until major cation and heavy and trace
metals analysis in the Geochemistry laboratory of the
NCE in Geology, University of Peshawar, Pakistan.
Another set of samples was collected in 500 ml
bottles and analyzed on spot for temperature (T), pH,
electrical conductivity (EC) and anions such as
chloride (Cl-) sulfates (SO4
2-), nitrates (NO3
2-) and
phosphates (PO4
3-) by using various instruments.
Instrumentation and Chemical Analysis
Temperature were determined by
thermometer and pH and EC by Hach pH and
conductivity meter. pH meter was calibrated with the
known buffer solutions and the EC was calibrated
with the 0.01M KCl. SO4
2-, NO3
2-, Cl- and PO4
3-
were determined on Hach DR/2000
spectrophotometer by using the Hach reagents
powder pillows of SulfaVer 4, NitraVer 5, Mercuric
thiocynide and PhosVer 3 respectively as
recommended by the American Public Health
Association (APHA) [11]. Fluoride was determined
by SPANDS method as recommended by APHA
[11]. In this method the water was first passed
through the Hach distillation apparatus and then run
on Hach DR/2000 spectrophotometer by using the
Hach SPANDS reagent solution. Major cations (i.e.,
Ca2+, Mg2+, Na+, K+, Fe2+, Mn2+) were measured by
flame while heavy and trace metals (i.e., Cu2+, Pb2+,
Zn2+, Cr3+, Ni2+, Cd2+) by the graphite-furnace
atomic absorption spectrometer (Perkin Elmer 3300,
HGA600) under the standard instrumental conditions
recommended by the manufacturer and with
background correction. Hollow cathode lamps were
used for respective elements. Air-acetylene was used
as fuel for flame atomic absorption spectrometer
(FAAS) while graphite tube with platform was used
in the graphite furnace atomic absorption
spectrometer GF-AAS. Certified stock standard
solutions purchased from Perkin Elmer PVT (Ltd)
were used for calibration purpose. Calibration curves
from the working standards of 0.2, 0.5, 1.0, 2.0, 5.0
and 10 mg/L of Ca2+, Mg2+, Na+, K+, Fe2+, Mn2+ and
0.05, 0.1, 0.2, 0.5 and 1.00 mg/L of Cu2+, Pb2+, Zn2+,
Cr3+, Ni2+, Cd2+ were prepared. The detection limits
of various elements are Ca: 1.5 µg/L , Mg: 0.15 µg/L,
Na: 0.3 µg/L, K: 3.0 µg/L, Fe: 5 µg/L, Mn: 1.5 µg/L,
Cu: 0.014 µg/L , Pb: 0.05 µg/L, Zn: 0.02 µg/L, Cr:
0.004 µg/L, Ni: 0.07 µg/L, Cd: 0.002 µg/L. The
accuracy of the method was determined by running
the triplicate samples, collected during field, having
standard deviation of <0.1% and also by preparing
the acid mixture blanks and by spiking the samples
with known concentrations of all cations determined
with mean recoveries of 90.5±1.2%.
All the reagents, chemicals and acids used
were of analytical grade (Merck, Germany). All the
glassware used were thoroughly washed in ultrasonic

MOHAMMAD TAHIR SHAH et al., J.Chem.Soc.Pak., Vol. 34, No. 1, 2012 250
bath and cleaned with the ultrapure distilled water
and kept for 3 hours in an oven at 110 ºC prior to use.
Conclusions
The water samples from the surface water
(i.e., rivers and streams) and subsurface water (i.e.,
tube wells, dug wells and springs) used for drinking
and domestic purposes by majority of the inhabitants
of D.I. Khan, were analyzed for the physio-chemical
parameters. The surface water is relatively rich in
both major cations and heavy and trace metals while
shallow water is rich in anions. Deep water showed
relatively lesser contents of analyzed contaminants. It
was found that the concentrations of TDS, NO3
2-,
SO4
2-, F-, Cl-, Fe2+, Pb2+, Ni2+ and Cd2+ in certain
areas of the D.I. Khan division were reaching to
toxicity level and may cause health related problems.
The source of this contamination could be geogenic
rather than anthropogenic [12-14].
Acknowledgment
We are thankful to the Director National
Centre of Excellence in Geology, University of
Peshawar for providing financial support and
laboratory facilities to complete this research.
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