Environ Earth Sci (2016)75:1486
DOI 10.1007/s12665-016-6302-1
ORIGINAL ARTICLE
Assessing the hydrogeochemistry and water quality
of the Aji-Chay River, northwest of Iran
Rahim Barzegar1 • Asghar Asghari Moghaddam1 • Evangelos Tziritis2
Received: 29 April 2016 / Accepted: 29 November 2016
Ó Springer-Verlag Berlin Heidelberg 2016
Abstract Aji-Chay River is one of the most important
surface reservoirs of northwest of Iran, because it passes
through Tabriz city and discharges to Urmia Lake, one of
the largest permanent salty lakes in the world. The main
objectives of the present study are to evaluate its overall
water quality and to explore its hydrogeochemical char-
acteristics, including the potential contamination from
heavy metals and metalloids such as Co, Pb, Zn, Cd, Cu,
Cr, Al and As. For this purpose, 12 water samples were
collected from the main river body and its tributaries within
Tabriz plain. The Piper diagram classified water samples
mainly into Na–Cl and secondary into Ca–HCO3 and
mixed Ca–Mg–Cl types, denoting a profound salinization
effect. The cross-plots showed that natural geochemical
processes including dissolution of minerals (e.g., carbon-
ates, evaporites and silicates), as well as ion exchange, are
the predominant factors that contribute to fluvial hydro-
geochemistry, while anthropogenic activities (industrial
and agricultural) impose supplementary effects. Cluster
analysis classified samples into two distinct clusters; sam-
ples of cluster B appear to have elevated electrical con-
ductivity (EC) values and trace metals concentrations such
as Co, Pb and Cd, while SiO2 and Zn are low in compar-
ison with the samples of the cluster A. The main processes
controlling Aji-Chay River hydrogeochemistry and water
quality were identified to be salinization and rock weath-
ering. Both are related with geogenic sources which enrich
& Rahim Barzegar
rm.barzegar@yahoo.com
1
Department of Earth Sciences, Faculty of Natural Sciences,
University of Tabriz, Tabriz, Iran
2
Soil and Water Resources Institute, Hellenic Agricultural
Organization, 57400 Sindos, Greece
river system with elevated values of Na?, Cl-, Ca2?,
Mg2?, K?, SO42- and EC as a direct effect of evaporites
leaching and elevated values of Pb and Cd as an impact
from the weathering process of volcanic formations.
According to the US salinity diagram, all of the water
samples are unsuitable for irrigation as having moderate to
bad quality.
Keywords Hydrogeochemistry  Water quality 
Trace metals  Aji-Chay River  Iran
Introduction
River water is the main source for households, irrigation
and industrial use in many countries worldwide; however,
their quality is frequently influenced by both natural and
anthropogenic factors (Zhang et al. 2010). In last decades,
river water quality has become an issue of concern due to
the effects on human health and ecological systems,
especially around urban areas (Qadir et al. 2008; Wang
et al. 2013). Many factors, such as atmospheric composi-
tion, geology, climate change, vegetation (or organic
matter decay), land use activities, discharge of industrial
and domestic effluents, may affect river water quality in a
significant way (Zhang et al. 2007, 2010; Yidana et al.
2008; Voutsis et al. 2015). Therefore, the evaluation of
hydrogeochemical characteristics is important and urgently
needed (Li et al. 2014; Jiang et al. 2015) in order to apply
water resources management plans and remediation
strategies.
The hydrogeochemical investigations on rivers provide
the essential information about environmental changes and
determine the ongoing geochemical processes (e.g.,
chemical weathering, redox transformations, ion exchange,
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sorption, etc.) by identifying the dominant controlling
factors (Dalai et al. 2002; Wu et al. 2008; Jiang et al.
2015).
River water contamination by trace metals is one of the
major quality issues and has not been improved along with
population and urbanization growth, especially for devel-
oping countries (Sundaray et al. 2006; Akoto et al. 2008;
Amadi et al. 2012). Apart from geogenic (natural) sources,
trace metals can disperse to the surface water via surface
runoff or discharge from industrial and domestic wastes,
agricultural sources (e.g., pesticides, herbicides and fertil-
izers), atmospheric deposition, and automobile emissions
(Smail et al. 2012). These metals can infiltrate to deeper
soil layers and eventually reach groundwater by leaching.
Therefore, the identification of contamination sources is
critical for water resources in order to limit the potential
adverse effects (Wu et al. 2009).
Previous studies have investigated hydrogeochemistry
of river systems in different areas around the globe by
using ion ratios and multivariate analysis. For example,
Edet et al. (2013) conducted a study on hydrogeochemistry
of the river systems in the southeastern Nigeria using cross-
plots, multivariate statistics and a water quality index. The
results showed that tidal flushing and dumping of domestic
and human waste into the river systems were the main
factors controlling the river water chemistry with little or
no contribution from silicate and carbonate weathering.
Song et al. (2011) applied multivariate statistical analysis
to evaluate water quality of a tributary of the Pearl River,
southern China. They concluded that most variables in the
agricultural/rural area were primarily influenced by
physicochemical and organic pollution, sewage pollution,
geogenic factor, agricultural non-point source pollution,
and accumulated pesticide usage while in the industrial/
urban area were related to industrial wastewaters, mineral
contamination, geogenic factor, urban sewage, and chem-
ical industrial pollution. Jung et al. (2016) evaluated the
water quality for the Nakdong River watershed using
multivariate analysis. The results indicated that the moni-
toring sites with high levels of contamination were mostly
those sites going through the heart of the city or the sites
affected by residential sewage directly, as well as the sites
located midstream and downstream of the Nakdong River.
Aji-Chay River is one of the most important rivers in the
northwest of Iran. Although the river water is used for
agricultural purposes and recharges the Tabriz plain aqui-
fer, very few studies dealt with the assessment of its
hydrogeochemistry, including Asghari Moghaddam et al.
(2014) who investigated the classification of Aji-Chay
River water quality for agriculture in the range of Tabriz
plain and Barzegar et al. (2016a) who developed wavelet–
artificial intelligence hybrid models for prediction of the
Aji-Chay River salinity. In an effort to cover that gap and
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Environ Earth Sci (2016)75:1486
provide critical information, the main objectives of the
present study are: (1) to evaluate the overall water quality
of the Aji-Chay River main streamline and some of its
branches at different locations in the Tabriz plain and (2) to
explore its hydrochemical characteristics including the
potential contamination derived from heavy metals and
metalloids such as cobalt (Co), lead (Pb), zinc (Zn), cad-
mium (Cd), copper (Cu), chromium (Cr), aluminum (Al)
and arsenic (As).
Materials and methods
Study area
The Aji-Chay River (37°240 –38°370 N, 45°300 –47°450 E) is
situated at East Azerbaijan province and east of Urmia
Lake, northwest of Iran (Fig. 1). The lowest and highest
mean daily temperatures are -22 °C in January and 40 °C
in July, respectively, with an annual average of 9 °C. The
mean annual precipitation is 230.7 mm for the period of
1989–2013 according to the data from Tabriz airport
meteorological station (Barzegar et al. 2016a).
The oldest geological formations are the Permian–Tri-
assic and Cretaceous limestone and metamorphic rocks that
occupy the northern part of the Morrow Mountain. These
formations are composed of pelitic schists, along with
limestones and quartzites all disturbed by post-Cretaceous
diabasic dikes as the igneous intrusions. The Miocene
series (Upper Red Formation) are the most important for-
mations in the study area and mainly occur in the north-
eastern part of the Tabriz region. These series consist of red
marls with gypsum, conglomerate, salts (such as sylvite,
epsomite and anhydrite) and marly limestones (Barzegar
2014; Barzegar et al. 2016b). The Plio-Pleistocene volcanic
tuffs are extended and conformably overlaid the Pliocene
beds to the south of the Tabriz plain around the core of the
Sahand Volcano (Moghaddam and Allaf Najib 2006). The
formation is composed mainly of red and green andesite
tuff admixed with large quantities of blocks, boulders,
gravel and sand of volcanic and alluvial origin (Asghari
Moghaddam 1991; Asadian and Eftekhar Nejad 1993). The
volcanic rocks of Sahand Mountain comprise principally
lava flow, domes and volcanic debris flow. These rocks are
basaltic andesite, andesite, dacite and rhyodacite (Pirmo-
hammadi et al. 2011).
The Aji-Chay River watershed covers an area of
*13,853 km2 and extends *276 km to the Urmia Lake
Delta. The Gomanab-Chay, Nahand-Chay and Alibay-
kandi-Chay rivers join to the Aji-Chay River from the right
bank side, and the Saeid Abad-Chay, Basmenj-Chay,
Mehran-Rood and Sard-Rood and Ansa-Rood rivers join it
from the left bank side (Fig. 1c). The Aji-Chay River and
Environ Earth Sci (2016)75:1486 Page 3 of 15 1486

Fig. 1 Location of (a) Iran,

(b) east Azerbaijan province;
and (c) geological formations of
the study area (adopted from
Asadian and Eftekhar Nejad
1993), land uses and sampling
locations

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1486 Page 4 of 15
its right-bank-side tributaries enter the Tabriz plain from
the north and cross the Upper Red Formations. Therefore,
fine suspended solid materials are transported during
periods of higher discharge and saline water is transported
during lower discharge periods (Shokri 2014). The left-
bank-side tributaries originate from the northern slopes of
the Sahand Mountains and contain fresh (recharge) water
(average electrical conductivity = 600 lS/cm), and
deposit coarse sediments into Tabriz plain (Asghari
Moghaddam 1991; Barzegar et al. 2016c). Aji-Chay River
is fed by the melted snow of the Bozgoush, Sahand and
Arasbaran Mountains and is one of the major resources for
recharge of the aquifers within Tabriz plain. The river is
divided into several branches due to smooth topographic
relief and eventually discharges to Urmia Lake at the end
of the plain.
Agriculture and industry are the main human activities
in the study area. Industrial activities are relatively inten-
sive in the west of Tabriz city. Numerous factories
including petrochemical, leather tanning, metal smelting
and food-processing are located in the study area (Fig. 1c);
hence, large amounts of wastewater are discharged to Aji-
Chay River. Fertilizers containing nutrients such as nitro-
gen are used excessively to increase production in the
agricultural lands. Although Tabriz Sewage Treatment
Plant treats most of the collected municipal and domestic
wastewater, a significant portion is released without treat-
ment to the Aji-Chay River, due to the currently low
capacity of the plant. Therefore, the river receives a con-
tamination load from both point and non-point sources.
Like many major river systems worldwide, the Aji-Chay
River and its tributaries are extensively used as a primary
water resource and receptor of waste disposals by indus-
trial, agricultural, and domestic activities. The river water
is used for irrigation of medium to high salt-tolerant crops
such as forage barley, alfalfa, sorghum, soya, etc. Hence,
the evaluation of the hydrogeochemical status and the
overall quality regime of Aji-Chay River system are of
paramount importance for the strategic water resources
management of the area and the protection of local popu-
lation and natural environment.
Water sampling and analysis
A total of 12 surface water samples from Aji-Chay River
along its main stream and branches in the Tabriz plain were
collected in July 2012. Samples were filtered through a
0.45 lm cellulose nitrate membrane in the field and col-
lected in polyethylene bottles; a smaller aliquot intended
for trace metal analyses was added 2 mL of HNO3 50%;
samples were transferred immediately to the laboratory and
stored in cool temperature. Acidification as pretreatment
was used to minimize adsorption, hydrolysis, and
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Environ Earth Sci (2016)75:1486
precipitation effects. Field blanks and duplicates were used
to ensure the accuracy of analytical results and to identify
field contamination problems. In situ parameters such as
pH and electrical conductivity (EC) were measured in the
field by portable instruments Metrohm 826 and HANNA
HI 9033 models. Na? and K? were analyzed by flame
photometer, SO42-, NO3-, F- and SiO2 by spectropho-
tometer and other cations (e.g., Mg2?, Ca2?) and anions
(e.g., HCO3-, Cl-) by manual titration at the Hydrogeol-
ogy Laboratory of the University of Tabriz. Trace metals/
metalloids such as Co, Pb, Zn, Cd, Cu, Cr, Al and As were
analyzed by atomic absorption method by Spectra AA 220
model atomic absorption with graphite furnace models
manufactured GTA110 Varian with a precision of
±0.1 lg/L at the Water Quality Control Laboratory of East
Azerbaijan Province.
The accuracy of the chemical analysis was checked by
the ion charge balance method (Eq. 1), where the total
concentrations of cations, Ca2? ? Mg2? ? Na? ? K?
(TCC) in milliequivalents per liter should equal to the total
concentrations of anions, HCO3- ? Cl- ? SO42- ?
NO3- (TCA) expressed in the same units. The difference
between the TCC and TCA was within the thresholds of
±5% (Domenico and Schwartz 1998).
 
ðTCC  TCAÞ
Cationanion balance ¼  100: ð1Þ
TCC þ TCA
Multivariate statistical analysis
Multivariate statistical analysis can help to organize and
simplify datasets and provide meaningful insight (Yidana
et al. 2008). In recent years, the multivariate statistical
techniques have been used widely in water quality
assessment (e.g., Kim et al. 2005; Papatheodorou et al.
2007; Tziritis 2014; Hassen et al. 2016).
Correlation analysis is a technique by which can be
determined the correlation coefficient between variables.
The strength and significance of the relationships are
important in measuring the relationships between two
variables. The strength is indicated by the correlation
coefficient (r), whereas the significance is expressed in
probability levels (p values). The larger the correlation
coefficient, the stronger the relationship, whereas the
smaller the p level, the more significant the relationship.
Cluster analysis (CA) is a multivariate technique whose
primary purpose is to assemble objects using predeter-
mined selection criteria and to classify objects in clusters
that exhibit high internal (within-cluster) homogeneity and
high external (between-clusters) heterogeneity (McKenna
2003). The levels of the similarity at which observations
are merged are used to construct dendrogram (Lokhande
et al. 2008). The dendrogram provides a visual summary of
Environ Earth Sci (2016)75:1486
clustering process, presenting a picture of groups and their
proximity, with a dramatic reduction in dimensionality of
the original data. In this study, hierarchical cluster analysis
(HCA) was performed using Ward’s method (Ward 1963).
The Ward method uses an intra-cluster variation to form
clusters, formed by maximizing the homogeneity within
each cluster (Hardle and Simar 2007). The Euclidean dis-
tance criteria were used as measure of distance, which is
one of the most commonly adopted practices. The Eucli-
dean distance usually provides the similarity between two
samples and a distance can be symbolized by the difference
between analytical values from the samples (Bhuiyan et al.
2011). The major advantages of multivariate statistical
methods in the hydrochemical analysis are able to interpret
the hydrogeochemical processes based on specific or
multiple factors; in addition, they are able to reveal the
hidden inter-variable relationships. In this study, statistical
analysis was performed with the software package SPSS
16.0.
Suitability of water quality for irrigation
The suitability of river water for irrigation was assessed
using US salinity diagram (USSL 1954). This diagram
relates the sodium adsorption ratio (SAR) with the EC of
water and classifies the samples into irrigation water cat-
egories, based on the combination of these two parameters.
EC is the measured salinity of water, and SAR is calculated
from Eq. (2) where concentrations are reported in mil-
liequivalent per liter.
Naþ
SAR ¼

ð2Þ
Ca2þ þ Mg2þ =2
In addition, irrigation suitability was assessed by using
water standards and recommendations (PSD 2008; FAO
1992) for pH and some toxic minor and trace elements
from Aji-Chay River and its tributaries.
Results and discussion
Physicochemical characteristics of the water
samples
The descriptive statistical parameters (minimum, maxi-
mum, median, standard deviation, skewness and kurtosis)
for the analyzed water samples are listed in Table 1. Water
samples have pH values ranging from 7.4 to 7.9 (median
value of 7.6) which indicate that the water is slightly
alkaline. EC which is an indirect measure of ionic strength
and mineralization of natural water showed large variation,
ranging from 1200 to 47,200 lS/cm (median value of
Page 5 of 15 1486
3450 lS/cm); the dominant causes of those values and
relative concentrations are mainly attributed to the impact
from irrigation water return flow and evaporites. The order
of abundance of the major cations is Na? [ Mg2? [ -
K? [ Ca2? and of major anions is Cl- [ HCO3- [ -
SO42-. Based on median values, trace metals and
metalloids follow the decreasing concentration order:
Al [ Zn [ Pb [ Co [ Cu [ Cr [ As [ Cd. High stan-
dard deviation was found for EC (±13,800 lS/cm) and Al
(±1100 lg/L) as a result of the wide variation of their
concentrations. Major ion concentrations in water samples
show much higher skewness and kurtosis than trace metals
indicating that that their statistical population is not fol-
lowing a normal (Gaussian) distribution. Values of these
statistics outside the range of -2 to ?2 indicated signifi-
cant deviations from normality (Wu et al. 2010).
Water type
The Piper (1944) and Stiff (1951) diagrams were used to
evaluate the hydrogeochemistry of the Aji-Chay River
water. The Piper diagram (Fig. 2) shows that most of the
water samples fall in the field of alkalies (Na?, K?)
dominating over the alkaline earth metals (Ca2?, Mg2?),
while the anions Cl- and SO42- dominate over CO32- and
HCO3-. The plot reveals that the water samples were
dominated by Na–Cl type and only two samples belong to
Ca–HCO3 and mixed Ca–Mg–Cl, respectively. Sample 12
with the Ca–HCO3 water type was collected from the outlet
of the Tabriz Petrochemical Company that discharges to
Aji-Chay River. Sample 6 belongs to mixed Ca–Mg–Cl
water type and was collected from the Mehran-Rood River
which is joined to Aji-Chay River. The other samples are
of Na–Cl water types and denote the significant impact
from evaporitic formations. Samples 4, 5 and 7 show the
highest Na–Cl content; the elevated salinity of the samples
4 and 5 is attributed to the evaporitic Miocene formations,
whereas salinity of sample 7 is attributed to man-made
effects from the industrial tanning process which is close to
the outlet of tanning factories. Sample 1 that shows the
lowest Na–Cl content was collected from the outlet of the
Tabriz Sewage Treatment Plant and its salinity is low due
to treatment process. The Stiff diagrams (Fig. 3) show that
the concentrations of the Na? and Cl- are high for all
samples except of samples 6 and 12. The diagrams illus-
trate that concentration of Na? and Cl- is significantly
elevated in samples 4, 5 and 7.
Cluster analysis
Cluster analysis (CA) was used to detect similar groups
between the sampling sites in the study area. Because the
original data sets do not follow a Gaussian distribution,
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Table 1 Analytical result for

Minimum Median Maximum Standard deviation Skewness Kurtosis
physicochemical parameters,
major ions and trace metals pH 7.4 7.6 7.9 0.1 0.7 2.4
EC (lS/cm) 1200.0 3450.0 47,200.0 13,800.0 2.2 5.0
Na? (mg/L) 141.5 640.0 10,400.0 3210.0 1.9 3.3
K? (mg/L) 4.2 2.0 56.9 13.1 1.9 5.4
Ca2? (mg/L) 73.7 1.3 961.6 249.0 2.7 7.8
2?
Mg (mg/L) 23.3 4.7 488.8 130.0 3.0 9.6
HCO3- (mg/L) 217.1 4.2 1.0 218.0 2.2 6.6
SO42- (mg/L) 106.0 2.7 2.9 900.0 1.9 2.8
Cl- (mg/L) 110.7 9.1 1.8 5340.0 2.3 5.9
F- (mg/L) 0.4 0.6 0.8 0.1 0.6 -16.8
SiO2 (mg/L) 1.3 2.1 4.6 0.8 1.9 4.9
NO3- (mg/L) 0.8 3.1 96.9 34.8 0.4 -1.3
Co (lg/L) 14.0 29.0 175.0 47.5 2.3 5.4
Pb (lg/L) 21.0 40.0 75.0 17.3 0.6 -0.2
Zn (lg/L) 10.0 41.0 110.0 31.9 0.6 -0.2
Cd (lg/L) 4.0 9.5 35.0 10.6 1.3 0.2
Cu (lg/L) 5.0 14.5 58.0 13.3 2.8 9.2
Cr (lg/L) 5.0 12.0 175.0 58.5 1.2 0.2
Al (lg/L) 67.0 698.0 4000.0 1100.0 2.1 5.5
As (lg/L) 0.8 10.5 46.0 15.0 1.0 0.1

Fig. 2 Piper diagram of the

water samples

log-transformation was considered essential; hence, the
datasets were subsequently normalized in order to avoid
erroneous interpretations (Vega et al. 1998; Helena et al.
2000). CA generated a dendrogram grouping the sampling
sites into two clusters; results are shown in Fig. 4. Cluster
A includes samples 1, 9, 2, 3, 12, 8, 11, 10 and 6, while
cluster B includes samples 4, 5 and 7. Samples of cluster A
are located in the Aji-Chay River mainstream (central and
western sampling sites), whereas samples of cluster B are
located in the eastern river sampling sites. As identified by
CA, Box and Whisker plots of the parameters showing
group differences are presented in Fig. 5. It can be resulted
that the sampling sites of the cluster B have elevated EC
values and concentrations of major ions, as well as of some

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Fig. 3 Stiff diagram of the water samples
Fig. 4 Hierarchical cluster analysis: dendrogram of water samples
trace metals such as Co, Pb and Cd; on the contrary,
samples showed low concentrations of SiO2 and Zn in
comparison with the sampling sites of the cluster A, which
can be attributed to dissolution of geological formations
(primary volcanic formations and secondary Miocene for-
mations) and anthropogenic activities, e.g., input from
sewage effluents. Samples of cluster A are mostly influ-
enced by geological formations, which are situated in the
Sahand Mountain and anthropogenic activities, e.g., agri-
cultural practices.
Correlation analysis
Pearson’s correlation analysis was adopted to reveal the
correlations between EC, pH, major ions and trace metals;
results are provided in Table 2. This was performed due to
Page 7 of 15 1486
the significance of variable’s correlation, as suggested by
previous studies (e.g., Stumm 1992; Appelo and Postma
2005; Wang et al. 2016) which indicated that the mobility
of trace metals adsorbed on various solid phases of sedi-
ments, including sedimentary organic matter, Fe–Mn oxi-
des, carbonate phases, and other minerals, is strongly pH
dependent. Trace metals are mobilized when pH values are
low, whereas they are entirely sorbed when pH values are
circum-neutral (Belzile et al. 2004; Balkhair and Ashraf
2016).
Due to the limited number of samples used for statistical
processing, the interpretation of the results was performed
with caution, bearing in mind the general geological and
hydrogeological conditions of the area, so as to avoid
misinterpretations due to statistical artifacts.
Based on the results, there is no significant correlation
between pH and the concentration of trace metals and
metalloids such as Co, Pb, Cd, Cr and As, suggesting that
pH is not the main factor affecting the mobility of these
metals in the river water. On the contrary, pH seems to
affect mobility of Zn, Cu and Al, by showing medium and
high correlation (r = 0.597, 0.603 and 0.832, respectively).
There is a strong correlation between EC and all major
ions except K? and HCO3- which suggests the contribu-
tion of these metals in the salinity of the water. The EC is
significantly correlated with the concentrations of some
trace metals including Co (r = 0.861, p \ 0.01), Pb
(r = 0.853, p \ 0.01) and Cd (r = 0.861, p \ 0.01), as
well as with some major ions like Na?, Mg2? and Ca2?. As
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Fig. 5 Box and Whisker plots for the physicochemical parameters of water samples (Clusters A and B)

123
 Table 2 Matrix of correlation coefficient for water variables
Environ Earth Sci (2016)75:1486

pH EC Na? K? Ca2? Mg2? HCO3- SO42- Cl- F- SiO2 NO3- Co Pb Zn Cd Cu Cr Al As

pH 1
EC -0.419 1
Na? -0.389 0.993 1
K? 0.044 0.16 0.235 1
Ca2? -0.37 0.947 0.938 0.248 1
Mg2? -0.447 0.960 0.924 0.000 0.951 1
HCO3- 0.004 0.016 0.026 -0.329 -0.276 -0.1 1
SO42- -0.263 0.848 0.862 0.071 0.651 0.718 0.498 1
Cl- -0.408 0.991 0.991 0.232 0.975 0.951 -0.094 0.791 1
F- 0.243 0.424 0.455 0.468 0.621 0.399 -0.639 0.119 0.511 1
SiO2 0.501 -0.753 -0.801 -0.451 -0.699 -0.613 0.073 -0.662 -0.781 -0.355 1
NO3- -0.229 -0.15 -0.144 -0.531 -0.357 -0.217 0.725 0.184 -0.221 -0.55 0.061 1
Co -0.318 0.861 0.865 0.328 0.967 0.859 -0.448 0.510 0.916 0.752 -0.710 -0.413 1
Pb -0.123 0.853 0.871 0.139 0.769 0.757 0.190 0.853 0.837 0.472 -0.620 0.024 0.725 1
Zn 0.597 -0.549 -0.572 -0.466 -0.529 -0.454 0.158 -0.366 -0.578 -0.159 0.688 0.125 -0.512 -0.253 1
Cd -0.266 0.861 0.902 0.295 0.717 0.693 0.309 0.941 0.840 0.315 -0.798 0.080 0.646 0.900 -0.515 1
Cu 0.603 -0.039 -0.055 -0.102 0.014 0.027 0.118 -0.017 -0.052 0.104 0.459 -0.237 -0.054 0.097 0.38 -0.085 1
Cr 0.003 0.072 0.086 -0.303 -0.165 -0.029 0.681 0.466 -0.009 -0.328 -0.132 0.596 -0.223 0.389 0.373 0.349 -0.218 1
Al 0.832 -0.238 -0.233 -0.139 -0.193 -0.212 0.127 -0.098 -0.247 0.226 0.511 -0.095 -0.180 0.130 0.774 -0.155 0.766 0.195 1
As 0.118 0.169 0.143 -0.133 0.303 0.267 -0.293 -0.082 0.200 0.328 0.267 -0.310 0.315 0.118 -0.122 -0.026 0.442 -0.551 0.141 1
Page 9 of 15
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addressed by the dominant water type (Na–Cl), salinization
is the main process that controls hydrogeochemistry of
river system. Based on land use activities and local geol-
ogy, the main source of salinization should be attributed to
the leaching of evaporitic formations, which are rich in
minerals containing Na?, Ca2?, Mg2?, Cl- and SO42-, like
halite (NaCl), calcite (CaCO3), gypsum (CaSO4), anhydrite
(CaSO42H2O) and sylvite (KCl).
Specifically, the correlation coefficient of SO42- with
Mg2? (r = 0.718, p \ 0.01) and Ca2? (r = 0.651,
p \ 0.05) suggests that the SO42- is mainly associated
with magnesium sulfate (e.g., epsomite) or gypsum/anhy-
drite. Na? shows strong correlation with Ca2? (r = 0.938,
p \ 0.01) and Mg2? (r = 0.924, p \ 0.01 indicating a
common source (e.g., evaporites and/or feldspars of vol-
canic rocks) for these ions. The significant correlation
between Ca2? and F- (r = 0.621, p \ 0.05) indicates the
effect of fluorite (CaF2) dissolution on the water chemistry.
The negative moderate correlation between K? and NO3-
suggest that K? is originated naturally, e.g., through the
dissolution of K-feldspars (KAlSi3O8). Nitrates show no
specific correlation with other parameters, apart from
HCO3- (r = 0.725, p \ 0.01). Hence, elevated values of
NO3- should be attributed to the excessive use of nitrogen
fertilizers [NH4NO3(CaCO3)] applied for farming, while
the covariance with bicarbonates may be an indication of
domestic effluent contamination (e.g., through direct dis-
posal or septic tanks).
Cl- should be possibly attributed to anthropogenic
sources, such as domestic effluents, fertilizers and septic
tanks, or from natural sources, such as dissolution of
chloride bearing minerals contained in the geological for-
mations (Jiang et al. 2015). The correlation of the Cl- with
Na? (r = 0.991, p \ 0.01), Ca2? (r = 0.975, p \ 0.01)
and Mg2? (r = 0.951, p \ 0.01) implies that the sources of
Cl- can be explained by dissolution of Cl-bearing minerals
such as halite.
The Pb and Cd appear elevated values (median = 40
and 9.5 lg/L, respectively) which are much higher than
those reported for natural waters (Hem 1985) and seem to
have a common source due to their high correlation
(r = 0.9, p \ 0.01). Based on the evidence so far, this
source cannot be exclusively related with the impact of
industrial activities. As seen in Fig. 1, the highest values of
Cd and Pb (samples 4 and 5) are far away from the radium
of impact of industrial units and upward from the natural
river flow which crosses this area (industrial area). There-
fore, Cd and Pb should originate from another source
which is possibly geogenic.
Since the geochemical analyses of parent geological
formations are not available, the estimation of Cd and Pb
enrichment sources is based on assumptions from geolog-
ical evidences in areas with similar characteristics. A
123
Environ Earth Sci (2016)75:1486
possible explanation is related with the weathering of
volcanic tuffs which predominate at the catchment sub-
strate. Leaching and re-mobilization of trace elements from
volcanic formations is a common process that depends on
the geochemical conditions and other physiographical
factors (e.g., climatic, hydrological etc.). As reported in
other studies, Pb can be mobilized by weathered andesites,
especially when catalyzed by bacterial actions (Fein et al.
1999). As seen in Fig. 1, the mountainous areas of the
basin are occupied by andesites and weathered andesitic
tuffs and other pyroclastic materials, whose weathered
products could enrich river water and contaminate by
natural flow the entire system.
Alternatively (or supplementary), Pb and Cd concen-
trations may originate from the leaching of evaporitic
formations. According to Rouvier et al. (1985), many
diapirs with evaporite successions in southern Europe and
North Africa are accompanied by strata-bound Pb–Zn
mineral deposits. Changes in geochemical conditions may
trigger re-mobilization of trace metals, which are contained
in the evaporitic bodies. This hypothesis is likely to occur,
but needs to be verified by the chemical analyses of
evaporates and their concentrations in the above metals.
An interesting fact is that Pb and Cd are strongly cor-
related with high salinities based on their EC values, as
well as with parameters (Na?, Ca2?, Cl-, SO42-, Mg2?)
observed at elevated concentration in saline waters. In
addition, based on correlation analysis, these parameters
are related with Pb and Cd, a fact that denotes a common
enrichment process or a synergetic action. Unless the origin
of Pb and Cd is related with evaporitic bodies as mentioned
before, a possible explanation is the co-enrichment of these
metals with major ions. The mechanism includes the
enrichment of river water with Pb and Cd due to andesitic
tuff weathering at the mountainous parts of the basin and
their subsequent salinization in the plain parts (where
evaporates prevail) due to evaporitic leaching. Hence, river
water is simultaneously enriched in both toxic metals and
major ions of different origin, but that eventually jointly
formulate the hydrogeochemical signature of Aji-Chay
River.
Finally, elevated concentrations of chromium may have
their origin at the industrial discharges of the area located
near site 7 (Fig. 1), since chromium salt is used as a by-
product in leather processing.
Processes controlling the river water chemistry
The Aji-Chay River crosses different geological formations
in the study area. Therefore, dissolution of different parent
materials leads to different combinations of ions to river
water system. For instance, generally Ca2? and Mg2?
mainly originate from the weathering of carbonates,
Environ Earth Sci (2016)75:1486
Fig. 6 a Plot of
(SO42- ? HCO3-) versus
(Ca2? ? Mg2?). b Plot of Na?
versus Cl-. c Plot of Ca2?
versus SO42-. d Plot of Na?/
Cl- versus EC (lS/cm) e Plot of
Na? versus (Ca2? ? Mg2?)
f Plot of (NO3- ? Cl-)/HCO3-
versus TDS (mg/L)
silicates, and evaporites, Na? and K? from the weathering
of evaporites and silicates, HCO3- from carbonates and
silicates, and SO42- and Cl- from evaporites (Jiang et al.
2015). Previous studies (e.g., Datta and Tyagi 1996; Kumar
et al. 2006; Venugopal et al. 2009) showed that if the
weathering and dissolution of calcite, dolomite, anhydrite,
and gypsum are the dominating processes in the water
system, therefore, the (Ca2? ? Mg2?) versus
- 2-
(HCO3 ? SO4 ) scatter plot will be close to the 1:1
equiline. As shown in Fig. 6a, most of the samples of
cluster A demonstrate the dissolution of calcite, dolomite,
anhydrite, and gypsum in the river water. The silicate
weathering can be indicated by the dominance of
(HCO3- ? SO42-) over (Ca2? ? Mg2?), whereas the
abundance of Ca2? ? Mg2? is an indicator of reverse ion
Page 11 of 15 1486
exchange (Elango and Kannan 2007; Barzegar et al.
2016c); however, in this study, most samples show a
dominance of (HCO3- ? SO42-) over (Ca2? and Mg2?).
Thus, the silicate weathering reaction influences the
chemistry of the Aji-Chay River. Additionally, the plot
shows that the water samples are distributed on both sides
of the 1:1 line, indicating that water mineralization is
controlled complementary to mineral dissolution by ion
exchange and reverse ion exchange processes. The plot of
(Ca2? ? Mg2?) versus Na? (Fig. 6e) was used to inves-
tigate the influencing of the ion exchange on the chemistry
of the river water. The plot shows the presence of the water
samples on either side of the 1:1 line indication that ion
exchange as well as some reverse ion exchange is also
taking place in the river water.
123
1486 Page 12 of 15
Fig. 7 Suitability of water samples for irrigation based on US salinity
diagram (USSL 1954)
The plot of Na? versus Cl- (Fig. 6b) was used to
evaluate the effect of halite dissolution on the river water
chemistry. The plot shows that the majority of samples fall
on the 1:1 equiline. This well-defined relationship and the
relatively high concentrations in Na? and Cl- demonstrate
the role of halite dissolution as a major process contribut-
ing to the water salinization (Appelo and Postma 2005).
Also, there is a positive correlation between Ca2? and
SO42- (Fig. 6c), reflecting that dissolution of gypsum/an-
hydrite is another major salinization process taking place in
the river water system.
If evaporation is the dominating processes in the water,
the plot of Na?/Cl- versus EC (lS/cm) would provide a
horizontal line (Barzegar et al. 2016c); similarly, if halite
dissolution is responsible for sodium, the Na?/Cl- molar
ratio should be approximately equal to 1, whereas a ratio
greater than 1 is typically employed to reflect Na? release
from a silicate mineral weathering (Meybeck 1987). The
molar ratios of Na?/Cl- for water samples range from 0.91
to 2.18 (Fig. 6d). The Na?/Cl- molar ratio in most water
samples are greater than 1, indicating that silicate weath-
ering is the effective process for Na? releasing to the river
water and the role of evaporation is insignificant.
123
Environ Earth Sci (2016)75:1486
Human activity is one of the most important factors
affecting river water quality. In addition to NO3-, other
ions such as Na?, Cl- and HCO3- are also contami-
nating water as a result of agricultural activity (using
manure and chemical fertilizers) (Jalali 2009). Therefore,
the elevated values of TDS can be an indication (Ell-
away et al. 1999; Gillardet et al. 1999). Han and Liu
(2004) and Jalali (2009) suggested that the high corre-
lation between TDS and (NO3- ? Cl-)/HCO3- reveals
the influence of anthropogenic activities on water
chemistry, especially those related with agriculture. As
shown in Fig. 6f, there is a strong positive correlation
(R2 = 0.9603) between TDS values and (NO3- ? Cl-)/
HCO3- for the samples of the cluster A which suggests
the influence of anthropogenic activities on the water
chemistry of the Aji-Chay River. Bearing in mind that
sample 7 is strongly influenced by anthropogenic factors,
it should not be considered with the other samples of
cluster B for correlation analysis and therefore being
excluded. In this case, any correlation attempt for cluster
B is not possible due to the limited number of samples
(2) used.
Evaluation of water quality for irrigation
The water samples were plotted on the US salinity diagram
(USSL 1954) to assess the quality of the river water for
irrigation. As shown in Fig. 7, the water samples include
three groups like Piper diagram illustrated in Fig. 2. Group
A of water samples fall in the field C3S1, C4S3, and C4S4.
Field C3S1 suggests low sodium concentration and high
salinity, indicating that this type of water can be used
practically for the majority of soil types with minimum
danger of exchangeable sodium (Aghazadeh and Asghari
Mogaddam 2010). Fields C4S3 and C4S4 indicate the
water with very high salinity hazard and high sodium
hazard, and very high salinity hazard and very high sodium
hazard, respectively. Group B fall in the field of C4S4.
Richard (1954) classified the quality of water as good,
moderate and bad for irrigation. According to this classi-
fication, all water samples are classified as moderate to bad
for irrigation. Excess salinity reduces the osmotic potential
of plants and thus interferes with the absorption of water
and nutrients from the soil (Saleh et al. 1999). However,
high salinity water can be considered for irrigation of
moderate and high salt-tolerant crops (Ravikumar et al.
2011).
As shown in Table 3, pH of the water samples is suit-
able for irrigation. The concentrations of NO3-, Co, Pb,
Cd, Cr and Al exceed Peruvian (PSD 2008) and FAO
(1992) guidelines for irrigation and therefore should be
monitored over time.
Environ Earth Sci (2016)75:1486
Table 3 Comparison of water quality standards for pH and concentrations of trace elements from Aji-Chay River
Parameters pH NO3- Co Pb
(mg/L) (lg/L) (lg/L)
Aji-Chay River 7.4–7.9 0.8–96.9 14–175 21–75
b a b a
Irrigation 6.5–8.5 30 50 50
a
FAO (1992)
b
PSD (2008)
Conclusions
The Piper diagram revealed that the water samples belong
to Ca–HCO3, mixed Ca–Mg–Cl and Na–Cl types,
denoting a profound salinization effect. The cross-plots
showed that natural geochemical processes including
weathering and dissolution of minerals (e.g., carbonates,
evaporites and silicates), as well as ion exchange, are the
predominant factors that contribute in fluvial hydrogeo-
chemistry, while anthropogenic activities (industrial and
agricultural) impose supplementary effects. CA classified
the sampling sites into two distinct clusters. The sampling
sites of the cluster B have high EC (also high concen-
trations of major ions) and some trace metals such as Co,
Pb and Cd and low SiO2 and Zn in comparison with the
sampling sites of the cluster A; this can be attributed to
the atmospheric inputs, dissolution of Miocene formations
and anthropogenic activities, e.g., input from sewage
effluents. The pH shows medium and high correlation
with Zn, Cu and Al metals (r = 0.597, 0.603 and 0.832,
respectively) indicating the effect of pH in mobility of
these metals. Salinization and rock weathering are the
main processes that control hydrogeochemistry of river
system. These processes are related with geogenic sources
which enrich river system with elevated values of Na?,
Cl-, Ca2?, Mg2?, K?, SO42- and EC as a direct effect of
evaporites leaching and possible effect from irrigation
water return flow. The elevated values of Pb and Cd may
have dual source, either as an impact from the Pb–Cd rich
minerals contained in the stratigraphy of evaporites or
(supplementary) from the weathering process of volcanic
formations. High Cr concentrations of the river water
originate from industrial discharges which chromium salt
is used as a by-product in leather processing. According
to the US salinity diagram, all of the water samples fall
into moderate and bad for irrigation. The concentrations
of NO3-, Co, Pb, Cd, Cr and Al exceed Peruvian and
FAO guidelines for irrigation.
Acknowledgements The authors would like to thank Mrs. Naeimeh
Kazemian, Mrs. Sima Shokri and Mr. Masoud Orouji for analyzing
the water samples and Mr. Mortaza Najib for his kind help in the
collection of data.
Page 13 of 15 1486
Zn Cd Cu Cr Al As
(lg/L) (lg/L) (lg/L) (lg/L) (lg/L) (lg/L)
10–110 4–35 5–58 5–175 67–4000 0.8–46
b a a a b
2000 10 200 100 5000 100a
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