Environ Geochem Health
DOI 10.1007/s10653-006-9080-y
ORIGINAL PAPER
Assessment of the chemical components of Famenin
groundwater, western Iran
Mohsen Jalali
Received: 23 February 2006 / Accepted: 1 December 2006

Springer Science+Business Media B.V. 2007
Abstract The Faminin area in the semi-arid
Hamadan state, western Iran is facing a serious
deficiency in groundwater resources due to an
increasing demand associated with rapid popula-
tion growth and agricultural development. The
chemical composition of 78 well samples through-
out the Faminin area was determined with the
aim of evaluating the concentration of the back-
ground ions and identifying the major hydrogeo-
chemical processes that control the groundwater
chemistry. The similarity between rock and
groundwater chemistries in the recharge area
indicates a significant rock-water interaction. The
hydrochemical types Na–HCO3 and Na–SO4 are
the predominate forms in the groundwater, fol-
lowed by water types Ca–HCO3 and Na–Cl. The
high values of electrical conductivity and high
concentrations of Na+, Cl–, SO2– –
4 and NO3 in the
groundwater appeared to be caused by the
dissolution of mineral phases and would appeared
to be caused by anthropogenic activities, such as
intense agricultural practices (application of fer-
tilizers, irrigation practice), urban and industrial
waste discharge, among others.
M. Jalali (&)
Department of Soil Science, College of Agriculture,
Bu-Ali Sina University, Hamadan, Iran
e-mail: Jalali@basu.ac.ir
Keywords Anthropogenic
Chemical
compo-sition
Groundwater
Hydrochemistry

Iran
Introduction
The continuing population growth in Iran is
rapidly depleting groundwater supplies in some
areas. Rapid industrialization and urbanization
have resulted in the degradation of soil and
groundwater and resulted in a shortage of water
resources of good quality in arid and semi-arid
zones. Groundwater is the primary source of
water for domestic, agricultural and industrial
uses in many countries, and one of the most
widespread forms of ground water contamination
in the world is salinization (Richer & Kreitler,
1993). In arid regions, agriculture is mainly limited
by the availability of suitable irrigation water. The
expansion of irrigation systems into such areas and
the inefficient use of groundwater in such systems
may lead to the salinization of groundwater.
Consequently, water quality and its management
have received much attention in developing
countries. Intense agricultural and urban devel-
opment has placed a high demand on groundwater
resources in arid and semi-arid regions of Iran
while putting these resources at greater risk to
contamination. Shallow groundwater from urban-
ized areas, on the other hand, has been declining
123

continuously, and groundwater quality in urban-
ized and agricultural areas has deteriorated in
recent years (Jalali, 2005b). The use of inorganic
fertilizer is a widespread agricultural practice in
Hamadan province, and it is common knowledge
that a high input of nitrogen fertilizers in intensive
agricultural practices is one of the main sources of
groundwater contamination.
Although groundwater in Iran is a very
important resource, little is known about the
natural phenomena that govern its chemical
composition or the anthropogenic factors that
currently affect these. The chemical composition
of groundwater is controlled by many factors,
including the composition of the precipitation,
geological structure and mineralogy of the water-
sheds and aquifers and the geological processes
within the aquifer (Andre, Franceschi, Pouchan,
& Atteia, 2005). The interaction of all factors
leads to various water types.
An understanding the geochemical evolution
of groundwater is important for a sustainable
development of water resources for the semi-arid
regions. Very little research has been conducted
with the aim of assessing the chemical compo-
nents of groundwater in Iran (Jalali, 2005c), and
limited information exists on the vulnerability of
the aquifer to pollution (Jalali, 2005b). The
Faminin area in the semi-arid state of Hamadan,
western Iran constitutes a major aquifer used for
drinking water and agriculture. Although this
aquifer system is intensively exploited, prior to
the present study little was known about the
major hydrogeochemical processes that control
the observed water chemistry. Similarly, the
origin of elevated concentrations of elements
and the vulnerability of the aquifer to pollution
were equally unclear.
A growing population and increased agricul-
tural and industrial activities in the area have
resulted in a deterioration of the water resources.
The groundwater in this area is affected by
salinization processes associated mainly with
intense groundwater exploitation for agricultural
activities. The investigation reported here is an
attempt to understand the major processes inter-
acting in this aquifer. To this end, the aims of this
study were to determine the origin, chemical
characteristics and the principal hydrochemical
123
Environ Geochem Health
processes controlling groundwater quality in
Famenin, western Iran by means of hydrogeo-
chemical analyses of the behaviour of major ions,
which may provide physical evidence for the
characterization process.
Materials and methods
Study area
The study area is in the region of Famenin city,
Hamadan province, and consists of an area of
about 700 km2 located between longitudes
4813¢39¢¢ and 4914¢37¢¢E and latitudes 3449¢
and 3514¢4¢¢N (Fig. 1). The basin is characterized
by hills in the southern parts, sloping towards the
north and northwest. The highest elevation (alti-
tude) in the hilly area is 1780 m a.s.l., whereas the
lowest altitude in the plains is 1650 m a.s.l. The
area has a cold temperate climate, with mean
maximum summer temperatures (July) of about
23.50C and minimum winter temperatures (Jan-
uary) of –1.90C. The climate of the study area is
considered to be semi-arid, with annual precipita-
tion of approximately 300 mm. Peak rain months
include January (30 mm), February (40 mm)
March (46 mm), April (41 mm), November
(38 mm) and December (40 mm). The late spring
and summer months are the driest, each with a
monthly rainfall below 5 mm (Sabziparvar, 2003).
Another feature characterizing the precipitation
in the study site is its irregular annual distribution.
The annual potential evaporation far exceeds the
annual rainfall with a mean annual amount of
approximately 1505 mm estimated from 1975 to
2001 (Sabziparvar, 2003). High evapotranspiration
rates result in the deterioration of groundwater
quality over time. The most important economic
activity in the area is agriculture, with the chief
crops being garlic, potato and wheat; actual
irrigation is lower than the total theoretical
demand as there is a considerable water deficit
in relation to the amount of land to be irrigated.
The Hamadan area is characterized by a pre-
dominance of metamorphic rocks of both sedi-
mentary and magmatic origins (Sepahi, 1999) and
the presence of the Alvand huge granitoid com-
plex. The metamorphic rocks constitute an assem-
Environ Geochem Health
Fig. 1 Study area showing the location of wells sampled for the groundwater analysis
blage of high to low metamorphic grade issued
from sedimentary sequences that have been
affected by a more or less developed tectono-
metamorphic event (Baharifar et al., 2004).The
northern parts of the study area are plain-like
regions, which are covered by Quaternary alluvial
sediments. Lower cretaceous carbonatic-volcanic
rocks, especially Oligo-Miocenc limestones, out-
crop in the northern part of the study area.
Most soils are highly calcareous and clayey and
are mostly classified as Aridisol. The predominant
clay minerals are illite, smectite, chlorite and
vermiculite (Jalali, 2005a).
Sampling method
Seventy-eight groundwater samples were col-
lected from Famenin area during the period 1–
22 September 2000 (Fig. 1). In order to avoid
contamination, clean 500-ml plastic containers
were used to draw the water samples from wells.
These containers had been rinsed with distilled
water before sampling. The samples were stored
in polyethylene containers, adequately labelled,
and preserved in the refrigerator until they were
taken to the laboratory for measurement.
Water analysis
Samples were analysed in the laboratory for the
major ions/compounds using standard methodol-
ogies. The pH and electrical conductivity (EC)
were measured on pH and electrical conductivity
meters, respectively. Calcium (Ca2+) and magne-
sium (Mg2+) were determined titrimetrically using
standard EDTA; chloride (Cl–) was determined by
standard AgNO3 titration; carbonate (CO2– 3 ) and
bicarbonate (HCO–3) were determined by titration
with HCl; sodium (Na+) and potassium (K+) were
measured by flame photometry; sulphate (SO2– 4 )
was determined by spectrophotometric turbidim-
etry; nitrate (NO–3) was determined by colourime-
try with an UV-visible spectrophotometer
(Rowell, 1994). Total dissolved solids (TDS) were
computed by multiplying the EC (dS m–1) by a
factor of 640. Care was taken that the pH and EC
and the HCO–3 and Ca2+ ions were analysed within
24 h of sampling. The quantity controls of the
measurements consisted of duplicate samples.
Saturation indices for calcite (SIcal), dolomite
(SIdol) and chemical facies were also computed
using the computer programmes PHREEQC and
AQUCHEM.
Results and discussion
Water quality
The statistical parameters, such as the minimum,
maximum, mean and standard deviation of
123
 Environ Geochem Health

Log pCO2e
different chemical compositions of the ground-
water samples, are shown in Table 1. The distri-

–2.24
–0.78
–3.08
0.43
bution patterns of the concentrations of different
parameters are shown as contour maps in Figs. 2–
4. Among the cations, the concentrations of Na+,

SI Calcite
Ca2+, Mg2+ and K+ ions ranged from 0.37 to 29.09,

0.44

0.27
–0.72
1.0
0.85 to 6.65, 0.25 to 5.55 and 0.003 to 3.54 mmol
l–1, with a mean of 7.76, 2.19, 1.55 and 0.1 mmol
l–1, respectively. Their concentrations (on the

SI Dolomite
basis of mmol l–1) represent on an average to
61.8, 21.7, 15.6 and 0.7% of all the cations,

0.85
2.28

0.59
–1.58
respectively. The order of abundance is Na+ >-
Ca2+ > Mg2+ > K+. For the anions, the concen-

SId Gypsum
trations of each of HCO–3, Cl–, SO2– –
4 and NO3 fall
between 2.02 and 10, 0.50 and 28, 0.17 and 9.75,

–1.62
–0.01
–2.59
0.51
0.16 and 2.04 mmol l–1, respectively, with a mean
of 5.21, 4.89, 2.14 and 0.64 mmol l–1. The order of
their abundance is HCO–3 > Cl– > SO2– 4 > NO3,
–

945.5

224.0
553.8
TDSc

3,168
–1
and they contribute on average (mmol l ) 45.7,
32.8, 14.7 and 5.8%, respectively, to the total
anion content. The electrical conductivity (EC)

7.68
8.42

0.37
pH

6.2
indicates the amount of material dissolved in Table 1 Chemical compositionsa (major elements) in the well water samples (78 samples)
water, and its values ranged from 0.35 to 5 dS
ECb

1.47
4.95
0.35
0.86
m–1, with a mean of 1.5 dS m–1. Total dissolved
solids ranged from 224 to 3168 mg l–1, with an
SO2–
4

2.14
9.75
0.17
2.25
average of 945 mg l–1. Average pH was 7.8, with
maximum of 8.4 and minimum of 6.8, indicating
NO–3

0.64
2.04
0.16
0.38
that the pH of the water samples is well within the
permissible drinking limits (7.0–8.5) of the World
HCO–3

Health Organization (WHO).

5.21

2.02
1.41

The common groundwater contaminant in the

10

area is nitrate NO–3. Nitrate is the most common

CO2–
3

form of nitrogen that occurs in surface and

0.11
0.70

0.19

Electrical conductivity (EC) is expressed in dS m–1

Total dissolved solids (TDS) is expressed in mg l–1
0

groundwater and because of its anionic form,

Log pCO2, Equilibrium partial pressure of CO2

NO–3 is very soluble and mobile in aqueous

4.89

4.83
0.5
Cl–

28

solution. It represents the oxidized end product

Concentrations are expressed in mmol l–1

in the nitrogen cycle of the atmosphere, vegeta-

7.76

0.37
5.64
29.09
Na+

tion, upper soil and soil water zones. Concentra-

tions of NO–3 are the result of different pollution
0.003

processes involving municipal wastewaters, fertil-

3.54
0.1

0.4
K+

izers and the application of agricultural pesticides,

among others. The highest NO–3 concentration
Mg2+

1.55
5.55
0.25
0.95

SI, Saturation index

levels were found in areas where large amounts of

N fertilizers (commonly urea, nitrate or ammo-
Ca2+

2.19
6.65
0.85
1.25

nium compounds) are used due to intensive

agricultural practices (Jalali, 2005b). Alkali
wastewaters are commonly used in parts of the
Average

Hamadan plains in the state of Hamadan to

Max
Min
SD

irrigate the sugar beet and wheat crops. Effluent

b

d
a

e
c

123
Environ Geochem Health

(a)35.3

Latitude (Degree)
35.2

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(b)
35.3

35.2
Latitude (Degree)

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(c)
35.3

35.2
Latitude (Degree)

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(d)
35.3

35.2
Latitude (Degree)

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

Fig. 2 Spatial distribution of Ca2+ (a), Mg2+ (b), K+ (c) and Na+ (d) (mmol l–1) in the groundwater

123
 Environ Geochem Health

(a)
35.3

Latitude (Degree)
35.2

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(b)
35.3

35.2
Latitude (Degree)

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(c)
35.3

35.2
Latitude (Degree)

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(d)35.3
Latitude (Degree)

35.2

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

Fig. 3 Spatial distribution of Cl– (a), HCO–3 (b), NO–3 (c) and SO2– –1
4 (d) (mmol l ) in the groundwater

123
Environ Geochem Health

(a)
35.3

Latitude (Degree)
35.2

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

(b)
35.3
Latitude (Degree)

35.2

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

Fig. 4 Spatial distribution of EC (dS m–1) (a) and TDS (mg l–1) (b) in the groundwater

from the power plant is saline and sodic, and its of the samples the concentration of NO–3 is above
disposal onto the soil and into surface waters is a the recommended guidelines of the WHO
serious environmental threat (Merrikhpour & (0.81 mmol l–1). The high concentration of NO–3
Jalali, 2005). In addition, the use of sewage sludge could be related to wastewater leakage from
has become inevitable for irrigation as a rapid industrial activities, urbanization and agricultural
means to compensate for increasing water practices.
demands in many arid and semi-arid regions. In
some parts of the arid and semi-arid regions in Hydrochemical facies
Iran, such as the Hamadan plains in the state of
Hamadan, sewage sludge constitutes an impor- The piper diagram (Fig. 5) constructed using
tant source of supplemental irrigation because of AQUCHEM Scientific Software shows the
an inadequate availability of fresh surface and relative concentrations of the different ions of
groundwater. The size of the area irrigated with analysed water samples. Five main groundwater
sewage sludge has been expanding as the volume groups were identified based on the concentra-
of sewage sludge increases (Jalali & Khanlari, tions of the major ions: Na–HCO3, Na–SO4,
2006). Ca–HCO3, Na–Cl and Mg–HCO3. The spatial
The lines of equal NO–3 concentrations are distribution of water types in the groundwater is
shown in Fig. 3c. The results indicate that in 31% illustrated in Fig. 6.

123
 Environ Geochem Health

Fig. 5 Piper diagram of

the groundwater samples
in the study area

Water-rock interaction processes To evaluate the hydrochemistry of the waters,

we calculated the equilibrium partial pressure of
Interactions between groundwater and host rocks CO2 (pCO2) and the saturation indices (SI) for all
are the main processes responsible for the of the samples using the computer geochemical
observed chemical characteristics of the ground- programme PHREEQC (Parkhurst & Appelo,
water in the study area. 1999), using calcite as an example:

35.3
Ca-HCO3 Mg-HCO3 Na-HCO3 Na-Cl Na-SO4
Latitude (Degree)

35.2

35.1

35

34.9

48.6 48.7 48.8 48.9 49 49.1 49.2 49.3 49.4

Longitude (Degree)

Fig. 6 Spatial distribution of water types in the groundwater

123
Environ Geochem Health

fCa2þ gfCO2 precipitate calcite and dolomite, while they

3 g
SIcalcite ¼ log
Ksp;calcite
where {Ca2+} and {CO2–
3 } are their respective
activities in aqueous solution, and Ksp,calcite is the
solubility product for calcite. Saturation indices
were calculated for calcite, dolomite and gypsum.
The saturation indices describe quantitatively the
deviation of water from equilibrium with respect
to dissolved minerals. If the water is exactly
ð1Þ are undersaturated with respect to gypsum
mineral.
As the saturation state indicates the direction
of the process, precipitation is expected for calcite
and dolomite and dissolution is expected for
gypsum (Appelo & Postma, 1996). The graphs in
Fig. 7 show the evolution experienced by the
saturation indices of calcite, dolomite and gypsum
in relation to increasing SO2– 4 content. Through-

saturated with the dissolved mineral, SI equals
zero; positive values of SI indicate saturation, and
negative ones indicate undersaturation (Appelo
& Postma, 1996; Drever, 1997). Nearly all of the
water samples were oversaturated with respect to
calcite and dolomite and undersaturated with
respect to gypsum, suggesting that these carbon-
ate mineral phases may have influenced the
chemical composition of the study area. The
results indicate that the waters are likely to
Saturation index (gypsum)
out the area, the water evolves from a state of
oversaturation in calcite and dolomite towards a
lower saturation state. The higher HCO–3 and
Ca2+ and Mg2+ concentrations will cause a greater
calcite and dolomite oversaturation, which could
eventually induce their precipitation. The solu-
tion will be close to equilibrium with respect to
gypsum due to the greater SO2– 4 and Ca
2+
levels
induced by the gypsum dissolution. The low
solubility of calcite and the common ion (Ca2+)

0
0 2 4 6 8 10 12
-0.5
-1
-1.5
-2
-2.5
-3
SO42- (meq l-1)
Saturation index (dolomite)

2.5
2
1.5
1
0.5
0
-0.5 0 2 4 6 8 10 12
-1
-1.5
-2
SO42- (meq l-1)
Saturation index (calcite)

2.5
2
1.5
1
0.5
0
0 2 4 6 8 10 12
-0.5
-1
SO42- (meq l-1)

Fig. 7 Plots of SO2–

4 concentrations versus the saturation indices of gypsum, dolomite and calcite. Equilibrium fields are also
indicated

123
 Environ Geochem Health

induced by gypsum dissolution will cause a Table 2 Correlation between some of the hydrochemical
greater calcite precipitation. parameters
The saturation state of water changes with the Variables Correlation coefficient
water flow with respect to calcite, dolomite and
gypsum. There is only a slight tendency for the Cl vs. Mg 0.57**
Cl vs. K 0.35**
calcite and dolomite saturation indices to decrease Cl vs. Na 0.85**
with SO2–4 salinity. The concentration of Ca
2+
and Cl vs. Ca 0.77**
alkalinity do not vary greatly with salinity in the HCO3 vs. Mg 0.45**
groundwater, suggesting that calcite saturation and HCO3 vs. Na 0.57**
HCO3 vs. Ca 0.37**
precipitation is limiting Ca2+ and HCO–3 accumu- HCO3 vs. K 0.23*
lation in these waters. The groundwater is generally SO4 vs. Ca 0.65**
undersaturated with respect to gypsum. Only one SO4 vs. Mg 0.71**
sample was found to approach gypsum saturation, SO4 vs. Na 0.73**
SO4 vs. K 0.53**
with SI = –0.01. Gypsum SI increases in proportion HCO3 vs. Ca + Mg 0.43**
to SO2–4 salinity (Fig. 7) due to the parallel accu- HCO3 vs. Ca + Na 0.50**
mulation of SO2– 4 in the water.
Cl vs. K + Mg 0.60**
The statistical parameters of the computed EC vs. Ca 0.69**
EC vs. Mg 0.81**
pCO2 values for the water samples are shown in EC vs. Na 0.83**
Table 1. These computed values vary between EC vs. K 0.34**
8.32 · 10–4 and 1.66 · 10–1, with a mean of 5.75 · EC vs. Cl 0.68**
10–3 (atm); as such, they are significantly higher EC vs. SO4 0.86**
EC vs. HCO3 0.54**
than that of the atmosphere (10–3.5 atm). Such EC vs. NO3 0.30**
elevated values suggest that the groundwater
*, **Significant at the 5 and 1% level of significance,
system is open to soil CO2 (Njitchoua, Dever, respectively
Fontes, & Naah, 1997). As the dissolved CO2 gas
pressure of the waters is higher than that of the
atmosphere, the waters are supersaturated with suggested value of 0.50. One-half of the carbonate
respect to carbonate minerals. products comes from the reaction of carbonic acid,
which is eventually supplied by atmospheric
Cation chemistry input and the decomposition of organic materials
in soils (Berner & Berner, 1987). This indicates that
Calcium calcite is the main source of Ca2+. The dissolution of
carbonate is an equilibrium process, which is
Compositional relations among dissolved species controlled by CO2 partial pressure. My calculations
can reveal the origin of solutes and the process that of the partial pressure of CO2 of the samples
generated the observed water compositions. The revealed that the pCO2 of the samples were higher
correlation coefficients among the chemical com- than atmospheric pCO2. This CO2 can be produced
ponents of the groundwater samples are shown in by the oxidation of organic matter and by root
Table 2. The abundance of carbonate rock in the respiration in the unsaturated zone, followed by
basin suggests that the dissolution of carbonate dissolution in the recharge water. A certain amount
minerals is the major source of Ca2+ and Mg2+ in the of CO2 could be the result of the hydration of urea
groundwater, whereas HCO–3 is produced by weath- that reached the unsaturated zone:
ering of silicate and carbonate minerals. The most
common weathering reaction in the case of carbon-

ate is simple dissolution (Drever, 1997; Zhang, COðNH2 Þ2 þ 3H2 O ¼ 2NHþ
4 þ 2OH þ CO2
Huang, Letolle, & Jusserand, 1995), giving a 1:2 ð2Þ
ratio of Ca2+:HCO–3 or a Ca+Mg:HCO3 equivalence
ratio of 1:1. The average molar ratio of Ca2+/HCO–3 In addition, to form bicarbonate by fixation of
measured in the groundwater (0.43) was close to the CO2, this anion is released by the dissolution of

123
Environ Geochem Health
calcite and the weathering of silicate minerals.
The average molar ratio of Ca2+ + Mg2+ to HCO–3
in the groundwater was 1:1.39, indicating that
almost 72% of the HCO–3 is related to Ca2+ and
Mg2+. The higher values indicate that excess Ca2+
and Mg2+ have been balanced by Cl– and SO2– 4 .
The low Ca2+ + Mg2+ to HCO–3 ratio indicates
that some other source of HCO–3 must be present
possibly from silicate weathering – in addition to
carbonate weathering. The abundance of carbon-
ate and dolomite rocks in the basin suggests that
dissolution of these minerals will add significant
amounts of Ca2+ and Mg2+ to the reservoirs. The
excess of Mg2+ may also result from the dissolu-
tion of Na+ and magnesium sulphate minerals.
Calcium and SO2– 4 ions in the groundwater are
provided partly by the dissolution of gypsum. The
correlation between Ca2+ and SO2– 4 (r = 0.65)
shows that most of the groundwater samples
deviate from the 1:1 line, indicating another
source of Ca2+. The Mg2+/Ca2+ ratio varied from
0.12 to 1.8, which strongly suggests a water
component in contact with dolomite. The higher
Mg2+/Ca2+ ratios may indicate a water component
with Mg2+ added by mineral exchange, perhaps
replacing Fe released by pyrite oxidation (Banks,
Burke, & Gray, 1997). The low Mg2+/Ca2+ ratio
indicates that the weathering of calcite containing
high concentrations of Ca2+ may be important.
In addition to the combined dissolution of
calcite, dolomite, gypsum and anorthite, weath-
ering of sulphide minerals may also control the
observed Ca2+ and Mg2+ concentrations. High
SO2–4 levels, in combination with high Ca
2+
and
2+
Mg concentrations, have frequently been
explained by the weathering of reduced pyrite
(Dalai, Krishnaswami, & Sarin, 2002). In general,
high SO2– 4 concentrations may be derived either
by sulphide or SO2– 4 weathering (Drever, 1997;
Stallard & Edmond, 1987). Thus, gypsum disso-
lution and pyrite weathering may both have
contributed to the SO2–4 load of the groundwater.
The good correlation between SO2– 4 and Mg
2+
(r = 0.43) (Table 2) suggests that a part of the
SO2–4 and Mg2+ may also be derived by the
weathering of a magnesium sulphate mineral.
Binary plots of (Ca2+ + Mg2+) versus (HCO–3 +
SO2–4 ) were examined to study the relative
importance of the different weathering processes.
If Ca2+, Mg2+, SO2– –
4 and HCO3 are derived from a
simple dissolution of calcite, dolomite and gyp-
sum, then a charge balance should exist between
the cations and anions. The plot (Fig. 8a) falls
below the 1:1 line, indicating that a portion of the
HCO–3 + SO2– +
4 must be balanced by Na and K .
+
Therefore, it can conclude that the above chem-
ical reactions are hydrogeochemical processes
occurring in the aquifers of the study area.
A plot of (Ca2+ + Mg2+) versus total cations
shows that most of the points lie below the 1:1
line (Fig. 8b). The average ratio of Na+ + K+/
total cations is 0.48 (Fig. 8c). The high ratio is due
to the evaporation and Ca2+ precipitation, which
increases the Na+ concentration. This ratio rep-
resents the upper limit of the silicate weathering
contributions of alkalis to the total cations of the
groundwater because there could be other evap-
orite Na+/K+ minerals, in addition to NaCl, which
can also contribute to the (Na+ + Mg2+) of the
groundwater (Pande, Sarin, Trivedi, Krishnaswami,
& Sharma, 1994). The (Ca2+ + Mg2+)/(Na+ + K+)
molar ratio in the silicates of the upper crust is
generally 1.0 (Taylor & McLennan, 1985). The
average value for the studied groundwater was
0.93, which indicates a silicate source. A positive
correlation was found between Ca2+ and NO–3
(r = 0.46) and K+ and NO–3 (r = 0.46). Gimenez
(1994) explained these relationships as a result of
processes developed after the application of nitro-
gen fertilizers. These processes add Ca2+ and K+ to
the water as a result of a likely cation exchange
between NH+4 and K+ and Ca2+. Nitrification is the
microbial oxidation of ammonium-N to NO–3 in the
unsaturated zone (Stumm & Morgan, 1996):

NHþ þ
4 þ 2O2 ¼ NO3 þ 2H þ H2 O ð3Þ
Greater mineralization is generally associated with
higher NO–3 concentrations in the groundwater.
Also, increased acidity during nitrification leads to
carbonate dissolution, with Ca2+ enrichment.
The contribution of K+ to the groundwater in
these samples is modest (see Table 1). The low
levels of K+ in natural waters are a consequence
of its tendency to be fixed by clay minerals and to
participate in the formation of secondary miner-
als (Mathess, 1982). Potassium showed a good
correlation (r = 0.47) with Cl–, indicating that the
123
 Environ Geochem Health

(a) 35
30

Ca2++Mg2+ (meq l-1)

25
20
15
10
5
0
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
HCO3-+SO42- (meq l-1)

(b) 25
Ca2++Mg2+ (meq l-1)

20

15

10

0
0 10 20 30 40 50 60
Total cations (meq l-1)

(c) 60
50
Na++K+ (meq l-1)

40
30
20
10
0
0 5 10 15 20 25 30 35
Total cations (meq l-1)

Fig. 8 Scatter diagram of Ca2+ + Mg2+ versus HCO–3 + SO2–

4 (a), Ca
2+
+ Mg2+ versus total cations (b) and Na+ + K+ versus
total cations (c) for groundwater of the study area

weathering of sylvite (KCl) partly controls the K+ identify the mechanisms for acquiring salinity
chemistry. A weak correlation between K+ and and saline intrusions in semi-arid regions (Dixon
other major ions suggest that K+ is derived mostly & Chiswell, 1992; Magaritz, Nadler, Koyumdjisky,
from K-feldspars or K-bearing minerals. One & Dan, 1981; Sami, 1992). The high Na+ and Cl–
possibility is illite, which occurs in the soils of the contents detected in certain samples of the
region (Jalali, 2005a) and can weather to produce present study may suggest the dissolution of
K+ ions. chloride salts. The dissolution of halite in water
releases equal concentrations of Na+ and Cl– into
Sodium the solution. A parallel enrichment in both ions
indicates the dissolution of chloride salts or
Sodium is the most prevalent of the cations reconcentration processes by evaporation. There
present. This high concentration of Na+ in the was a high correlation between Cl– and Na+
groundwater can be attributed to the cation (r = 0.85) in the groundwater samples, but ana-
exchange and to the human activities. High lytical data deviate from the expected 1:1 relation,
concentrations of Na+ in irrigated areas are also indicating that most of the Na+ is derived from
the result of the repeated use of water. The other processes. There was a high correlation
Na+–Cl– relationship has often been used to (r = 0.97) between Na+ and SO2– 4 , indicating that

123
Environ Geochem Health
the excess of Na+ in these samples mostly result
from dissolution of sodium sulphate minerals.
The average molar ratio of Na+ to HCO–3 is 1.49.
Most of the groundwater samples deviated from
the 1:1 relation, indicating another source of Na+.
Dissolution of carbonate minerals is an equilib-
rium process which is controlled by CO2 partial
pressure. Bicarbonate, formed by the neutraliza-
tion of CO2, originated either by adsorption from
the atmosphere or from the decomposition of
organic matter in the recharge area. Weathering
of silicates in the sediments of the study area
would also release HCO–3 into groundwater.
Another possible mineral source of HCO–3
includes the dissolution of feldspars. A 1:1 rela-
tion between HCO–3 and Na+ plus K+ results when
HCO–3 is the result of K- and Na-feldspar disso-
lution (Tesoriero, Spruill, & Eimers, 2004). The
relationship between Na+ plus K+ and HCO–3 does
not adequately fit the 1:1 relation (r = 0.35) that
would be expected for the dissolution of Na- and
K-feldspars.
The ionic relations suggest that Ca2+ and Mg2+
provided by calcite, dolomite and gypsum disso-
lution are replaced by Na+ from a source other
than NaCl. Some of the Na+ may be derived from
other Na-bearing silicate minerals, such as albite
(Stallard & Edmond, 1987). The weathering of
albite produces kaolinite and Na+ ions (Smolders,
Hudson-Edwards, Van der Velde, & Roelofs,
2004).
A Na+/Cl– molar ratio greater than one is
typically interpreted as reflecting Na+ released
from silicate weathering reactions (Meybeck,
1987). It is probable that silicate dissolution is a
source of the Na+ in the groundwater in the
studied area. Among the rock-forming minerals
involved in hydrolysis, sodium plagioclase is
perhaps common and important. The average
molar ratio of Na+/Cl– (1.77) indicates much
higher Na+ values than those of Cl–. The Na+/Cl–
ratio in most groundwater samples (88%) is more
than one, indicating that Na+ release from silicate
weathering is important in the study area.
Common rock does not have a significant
amount of Cl–. The relatively high contribution
of Na+ to the total cations indicates that silicate
weathering and/or contributions from alkaline
soil groundwater are significant.
The cation exchange between Ca2+ or Mg2+
and Na+ may also explain the excess Na+
concentration (Stimson, Frape, Drimmie, &
Rudolph, 2001). Those samples with a Na+/ Cl–
ratio higher than one also show a deficit in Ca2+
+ Mg2+, and this would be consistent with a Ca2+–
Na+ cation exchange process leading to a soften-
ing of the water (Hidalgo, Cruz-Sanjulian, &
Sanroma, 1995; Hidalgo and Cruz-Sanjulian
2001). A Na–HCO3 water type is usually an
indication of cation exchange processes (Tijani,
2004), and this type of water is usually referred to
as exchange waters, implying that there is more
HCO–3 than the available alkaline-earth cations
(Ca2+ + Mg2+) in equivalent concentrations
(Tijani, 2004). These excess HCO–3 ions then
cause a release of the alkali ions (usually Na+)
into the solution by the exchange reaction with
the exchange sites.
To test the possibility that cation exchange
significantly affects groundwater compositions,
plots of Ca2+ + Mg2+ – HCO–3 – SO2– 4 as a function
+
of Na + K – Cl + –
was examined (Fig. 9).
Na+ + K+ – Cl– represents the amount of
Na+ + K+ gained or lost relative to that provided
by the dissolution of chloride salts (mostly halite
dissolution), while Ca2+ + Mg2+ – SO2– 4 – HCO3
–
2+ 2+
represents the amount of Ca and Mg gained or
lost relative to that provided by gypsum, calcite
and dolomite dissolution. In the absence of these
reactions, all data should plot close to the origin
(McLean, Jankowski, & Lavitt, 2000). If these
processes are significant in the composition con-
trolling process, the relation between these two
parameters should be linear, with a slope of –1.
Figure 9 indicates that an increase in Na+ + K+ is
related to a decrease in Ca2+ + Mg2+ or an
increase in HCO–3 + SO2– 4 . All data plot, as
expected, close to a straight line (r = 0.965), with
a slope of –0.949; this clearly points to the
existence of cation exchange (Garcia, del v
Hidalgo, & Blessa, 2001; Jalali, 2005c). Thus, ion
exchange is also responsible for the increase in
Na+ from the recharge zone to the discharge zone.
Major ion evolution sequence
A simple major ion evolution sequence in
groundwater along its flow path has been
123
 Environ Geochem Health

14.00

Ca 2++Mg 2+-SO 4 2--HCO 3- (meq l-1 )

12.00
10.00
8.00
6.00
4.00
2.00
0.00
-15.00 -10.00 -5.00 -2.00 0.00 5.00 10.00
-4.00
-6.00
K++Na+-Cl- (meq l-1)

Fig. 9 Plot of Ca2+ + Mg2+ – SO2– – + + –

4 – HCO3 and Na + K – Cl in the groundwater of the study area

reported and described in many areas worldwide mately the same proportions in the groundwater,
(Freeze & Cherry, 1979; He, Stober, & Bucher, suggesting that they are relatively conservative
1999). The groundwater from the study area species and good indicators of solute accumula-
evolves along the flow path. Based on the tion by evaporite dissolution or evapoconcentra-
principal component of the water samples, two tion of the recharge water (Banks et al., 2004).
main zones were recognized in the study area: Alkalinity and Na+, Cl– and SO2– 4 all were in
recharge zone and discharge zone. The vertical higher concentrations in the discharge area. This
infiltration of meteoric water, surface water and is likely to be related to the greater degree of
irrigation water are the major pathways for evapoconcentration of solutes in the lowland
groundwater recharge. Immature highland areas and the greater degree of microbial pro-
groundwater is dominated by Ca2+; Mg2+ and ductivity in lowland soils, leading to higher
HCO–3 ions resulting from the dissolution of alkalinity (Banks et al., 2004). Topography is
carbonate and hydrolysis of aluminosilicate min- generally lower in the discharge area, resulting
erals basically control the chemistry of waters in in slower groundwater flow; the water conse-
the recharge area. In the discharge area, HCO–3 quently remains underground longer and is a
and Na+ are the prevailing ions, representing more hydrogeochemically mature groundwater
cation exchanged waters. The chemistry of the (Banks et al., 2004). Thus, under arid conditions,
waters in this area is affected by direct cation high evaporation would dramatically affect the
exchange, where Na+ existing in the clay fraction groundwater chemistry in the discharge area,
of the aquifer material is exchanged for Ca2+ in resulting in more higher levels of Na+ and Cl–
the groundwater (Appelo & Postma, 1996). In than those found in the transition and recharge
this area, evapoconcentration in the discharge areas (Adams, Tredoux, Harris, Titus, &
zone and the dissolution of evaporites progres- Pietersen, 2001; Plummer, Busby, Lee, & Han-
sively increase salinity. Anion composition shaw, 1990; Sikdar, Sarkar, & Palchoudhwy, 2001).
changes from HCO–3 to Cl––SO2– 4 . The cation The discharge zone is the agricultural region of
composition of the water changes from Ca2+– the study area. Agriculture has both indirect and
Mg2+ to Na+. Correspondingly, the precipitation direct effects on the quality of surface and
of calcite occurs, and the water type evolves from groundwater and is one of the key activities
Ca–Mg–HCO3-type via Ca–Mg–SO4–HCO3-type causing water quality degradation in many parts
to the Na–HCO3–Cl and Na–SO4–Cl type. of Iran. Municipal and industrial wastewaters are
The less saline samples tend to be dominated not properly treated before discharge, which
by Ca–(Mg)–HCO3, while the more saline ones makes it easy for contaminants to reach the
are dominated by Na–SO4–Cl. There are signif- groundwater. Arid conditions create irrigation-
icant variations in the compostion of the water. return flow to become concentrated in some
Sodium, Cl– and SO2– 4 all increase in approxi- chemical constituents because of a number of

123
Environ Geochem Health
processes, such as evapotranspiration, mineral
dissolution, fertilizer application and agricultural
residues (Cardona, Carrilo-Rivera, Huizer-
Alvarez, & Graniel-Castro, 2004). The net loss
in Ca2+ and HCO–3 is a common result of
precipitation accompanied by a net gain of Na+,
K+, Cl–, SO2– –
4 and NO3 (Richter & Kreitler, 1993).
The groundwater is contaminated with NO–3 in
this zone. Recent studies have indicated that
there is strong relationship between land use and
the quality of groundwater in the area (Jalali,
2005b). The framer surveys indicate that exces-
sive N application often up to two- to threefold
the recommended rate is very common in vege-
tables crops (Jalali, 2005b). Fertilizer application
is carried out in the autumn or spring. Most of the
fields are flood irrigated, with poorly managed
irrigated systems, resulting in low irrigation effi-
ciency. Therefore, large amounts of N fertilizer
and an inadequate management of N fertilization
coupled with low irrigation efficiency are mainly
responsible for the NO–3 concentrations in the
groundwater (Jalali, 2005b). This means that
changes in land use and management practices
can have a considerable impact on the water
quality parameters.
Salinity is the total amount of inorganic solid
material dissolved in any natural water, and water
salinization refers to an increase in TDS and in
the overall chemical content of the water (Ritcher
& Kreitler, 1993). Changes in groundwater salin-
ity and the overall chemical composition occur
along flow paths from the recharge to the
discharge area due to either natural and/or
anthropogenic causes (Ritcher & Kreitler, 1993).
Water that enters the soil is subject to chemical,
physical and biological changes. Several hydro-
chemical processes, including the movement of
groundwater through rocks containing soluble
mineral materials, the concentration of water by
evaporation and industrial and municipal waste
disposal, may cause an increase in the level of
dissolved solids. Moreover, irrigation with waste-
water (in some parts of the study area), which is
more saline than regional groundwater, increases
the rate of salinization of the groundwater.
Groundwater classifications based on TDS
(Freeze & Cherry, 1979) indicates that 23% of
the samples were brackish water (1000–10,000
mg l–1) with TDS values ranging from 224 to
3168 mg l–1. Most of the fields are flood irrigated,
with poorly managed irrigated systems, resulting
in low irrigation efficiency. The fields are irrigated
mainly during the late spring and summer
months, and the overall amount of water applied
to a field has been estimated to be 1000 mm
year–1. Within the study area, the salt loading
resulting from the application of groundwater for
irrigation having 224–3,168 mg l–1 of TDS would
be 2–32 Mg ha–1 year–1. The relatively high salin-
ity may be due to the lithologic composition of
these localities in addition to the leaching and
dissolution of the soil salts and the addition of
chemical fertilizers by the irrigation waters.
The high level of salinity in the irrigation water
reduces crop yield, and irrigation water must be
applied in excess quantities to leach the salts from
the soil. In addition to salinity, high concentra-
tions of Na+ are undesirable in the water because
Na+ adsorbs onto the soil cation exchange sites,
causing soil aggregates to disperse, thereby
reducing its permeability (Tijani, 1994). The
problem of Na+ is most severe with montmoril-
lonitic soils and least with kaolinitic ones.
Another property related to the Na+ hazard of
irrigation waters is the HCO–3 concentration.
Bicarbonate toxicities associated with some
waters generally arise from deficiencies of iron
or other micronutrients caused by the resultant
high pH (Bohn, McNeal, & O’Connor, 1985).
The weathering of minerals is of prime impor-
tance in controlling groundwater chemistry.
Gibbs (1970) suggested that a simple plot of
TDS versus the weight ratio of Na+/ (Na+ + Ca2+)
could provide information on the relative impor-
tance of the major natural mechanisms control-
ling groundwater chemistry: (1) atmospheric
precipitation, (2) rock weathering and (3) evap-
oration and precipitation. A Gibbs plot (Fig. 10a)
of data indicates that the groundwater chemistry
is mainly controlled by rock weathering and
evaporation and precipitation. The processes of
groundwater salinization are also often identified
from ionic versus TDS plots, such as Na+/Cl–
versus TDS or Cl – (Fig. 10b, c) (Mercado, 1985).
Chloride is chemically conservative and is often
used to monitor water quality changes (Ritcher &
Kreitler, 1993). Fresh groundwater in the
123
 Environ Geochem Health

(a) 100000
Evaporation dominance
10000

TDS (mg l-1)

evaporation-precipitation

1000

Rock dominance
100

10
Rainfall dominance

1
0 0.2 0.4 0.6 0.8 1
Na+/(Na++Ca2+)

(b) 6
5
Na+/Cl-

4
3
2
1
0
0 5 10 15 20 25 30
Cl (mg l-1)

(c) 6
5
Na+/Cl-

4
3
2
1
0
0 500 1000 1500 2000 2500 3000 3500
TDS (mg l-1)

Fig. 10 A Gibs plot: a indicating the mechanisms that determine the major composition of groundwater in the studied area,
b plot of Na+/Cl– versus Cl–, c Na+/Cl– versus TDS

recharge area increases in salinity in a gradient evaporation processes; contributions from other
towards the discharge areas. sources, such as cation exchange of Na+ for Ca2+
and Mg2+ and the weathering of aluminosilicates,
also contribute to the content of Na+. In addition,
Conclusions industrial or agricultural activities contribute to
the increases in Na+ concentration. Rock weath-
The major cations in the studied groundwater ering and anthropogenic-induced calcite dissolu-
are, in decreasing order of prevalence, Na+ tion is the main factor for the total increase of
Ca2+ > Mg2+ > K+. The major anions present are, Ca2+ in the groundwater. The application of
in decreasing order of prevalence, HCO–3 > Cl– fertilizers was found to enhanceNH+4 inputs into
> SO2–4 . In general, a significant increase in the the unsaturated zone. The nitrification of NH+4 in
degree of water mineralization was observed in the unsaturated zone is accompanied by proton
the direction of the water flow. The least miner- production that simulated the dissolution of
alized water was found closest to the main carbonate and provided an additional enrichment
recharge area. The hydrochemical types Na– of Ca2+ to the groundwater. The major ion
HCO3 and Na–SO4 dominate the largest part of evolution sequence of the groundwater from the
the study area. The high concentration of Na+ study area suggests that the chemical evolution of
is controlled mainly by rock weathering and the recharge area was controlled mainly by

123
Environ Geochem Health
processes of water-rock interaction. In the dis-
charge areas, salts concentrated in the unsatu-
rated zone, the dissolution of salts in the
saturated zone and the effluents related to
anthropogenic activities progressively increased
the salinity. The Na–SO4 and Na–Cl water types
are associated with high NO–3 pollution, reflecting
the degree of human influence. The use of N
fertilizers in the intensively cultivated area of the
study area contributes to the increase in the
concentration of NO–3 suggesting that changes in
land use and management practices might have
considerable impact on water quality parameters.
Acknowledgements Two anonymous reviewers made
valuable comments on the manuscript. The author
gratefully expresses his gratitude for their thoughtful and
thorough reviews.
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