Environmental Earth Sciences (2018) 77:45

https://doi.org/10.1007/s12665-017-7197-1

ORIGINAL ARTICLE

Using hydrochemistry and environmental isotopes in the assessment

of groundwater quality in the Euphrates alluvial aquifer, Syria
Zuhair Kattan1

Received: 28 February 2017 / Accepted: 29 December 2017

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Hydrochemical and environmental isotope methods were used to characterize the groundwater quality in ten wells belong-
ing to the Euphrates alluvial aquifer in Syria, with the aim to assess the origin and dynamic of groundwater salinization in
this system. The Euphrates River (ER) water along its entire course in Syria is rather fresh (TDS < 0.5 g/L), and thus, it is
suitable for drinking and irrigation purposes. Groundwater salinity progressively increases from north to south, changing
from almost freshwater (TDS < 0.6 g/L), with a Ca–Mg and ­HCO3 type near the Syrian–Turkish border to brackish water
(1 < TDS < 3 g/L), with a Ca–Mg or Na–Ca–Mg and S ­ O4–HCO3 type in the vicinity of Al-Raqqa, and hence it can safely be
used for irrigation. Downstream Deir-Ezzor the groundwater quality becomes fairly saline to very saline (3 < TDS < 29 g/L),
with a Na–Cl type, and therefore it has an absolute hazard (SAR > 5) for irrigation uses. This pattern of chemical evolu-
tion, which is also clearly reflected in the variations of groundwater ionic ratios, completely agrees with the thermodynamic
simulation results obtained by an experimental evaporation essay of a water sample taken from the ER near Deir-Ezzor.
Stable isotopes permit the distinction between three main evaporation processes: under high, intermediate and low humidity
conditions. Radioisotopes (3H and 14C) indicate the recent age and renewability of groundwater in this aquifer and confirm
that its origin is entirely belonged to the ER water, either by direct bilateral interconnection or by vertical infiltration of the
irrigation water totally taken from the ER. Relationships between major ions and δ18O values of the groundwater allow to
differentiate between two main enrichment processes: either evaporation only or evaporation plus dissolution, that can explain
altogether the development of groundwater salinity in such a dry area.

Keywords  Hydrogeology · Groundwater · Hydrochemistry · Environmental isotopes · Salinity · Euphrates river basin ·
Syria

Introduction Li et al. 2016). By assessing the physical, chemical, bio-

Water quality is generally the results of diverse natural and
anthropogenic factors. Domestic pollution (point and non-
point), land use, floods, drought, forestry practices, mining,
power generation, intensive groundwater extraction and the
wildlife of an area can potentially create tremendous risks to
both surface and groundwater quality (Icaga 2007; Kazi et al.
2009; Lockhart et al. 2013; Vystavna et al. 2015). Assess-
ment of water quality is the first step in any evaluation and
management of a water resource (Todd 1980; Stadler 2012;
* Zuhair Kattan
cscientific3@aec.org.sy
1
Department of Geology, Atomic Energy Commission
of Syria (AECS), P.O. Box 6091, Damascus,
Syrian Arab Republic
logical and radiological behaviors against a set of selected
standards (WHO 2008), it is then possible to decide whether
water is suitable and safe for any of the different (domestic,
industrial and agricultural) uses.
Problems related to deterioration of groundwater quality
are frequent serious issues in many countries around the
world. Groundwater deterioration is known as a complex
phenomenon that may be due to combination of several
factors: saltwater intrusion into fresh aquifers (Lee 2005),
natural flushing of accumulated soil salts into good qual-
ity groundwater (Drever 1977), migration of saline water
formed from dissolution of natural rock salts toward fresh-
water-bearing systems (Johnson 1981; Panno et al. 2006),
infiltration of polluted saline water from agricultural activi-
ties and its mixing with fresh groundwater of phreatic aqui-
fers (Vengosh and Rosenthal 1994; Koh et al. 2010; Horst

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et al. 2011) and intensive over-pumping of limited ground-
water in deep aquifers (Khouri 1993). Irrigation under high
evaporation conditions, such as those prevailed in arid
and semiarid areas, also could enhance the salinization of
groundwater (GERSAR-SCET 1977). Groundwater saliniza-
tion in such cases is mostly due to a sharp rise of the shallow
groundwater table to certain depths, facilitating hence upper
movement of water by capillarity, and thus the formation
of soluble salts on the land surface. The later dissolution
of accumulated salts by irrigation water and its drainage
toward the water table progressively increases the ground-
water salinity (Dosso 1980). This problem, which is of a
particular concern because it can limit the socioeconomic
development in many areas, continues to attract the atten-
tion of scientists seeking for preservation and protection of
groundwater quality.
The environmental isotopes (2H, 3H, 18O, 13C, 14C, 15N
and 34S) are impressively valuable natural tracers that are
successfully used for comprehensive understanding of the
hydrological cycle and water geochemistry (Fritz and Fontes
1980; Rosanski et al. 1993; Clark and Fritz 1997; Kend-
all and McDonnell 1998; Criss 1999; Mook 2001; IAEA
2005; Carrasco-Cantos 2015). The importance of the stable
isotopes (2H and 18O) in such studies is due to their physi-
cal properties as principal members of the water molecule,
and thus sensitively respond to the various modification
processes, such as those occurred through the isotopic frac-
tionation during condensation and evaporation under dif-
ferent temperatures (Majoube 1971; Gonfiantini 1986). The
use of these isotopes in groundwater assessment studies has
proven to be a valuable tool for solving a number of hydro-
logical problems. Stable isotopes can effectively be used to
characterize the mixing between different waters, tracing the
direction of groundwater movement, determining the release
of irrigation waters and induced percolation in sediments,
detecting the soil salinity sources and origin of saltwaters in
groundwater-based irrigation schemes, and estimating the
contribution of irrigation return flows and agrochemicals to
groundwater (Payne et al. 1979; Simpson and Herczeg 1991;
Vengosh and Rosenthal 1994; Kattan 2008).
Salinization of groundwater in the vicinity of the Euphra-
tes River (ER) is an ongoing phenomenon, mainly devel-
oped after the construction of the Euphrates dam. Based on
the negative consequences of this critical problem, vastly
recognized in the downstream valleys of the ER, a number
of hydrodynamic, geochemical and isotopic investigations
were previously conducted in this riverine system (GER-
SAR-SCET 1977; Dosso 1980; Kattan and Najjar 2005;
Kattan, 2008, 2012, 2015). This study, which was started
within the IAEA-ARASIA regional project (RAS/7/027),
entitled “using environmental isotopes and natural radioac-
tivity in the assessment of groundwater quality,” that aimed
to assess the groundwater quality in the Euphrates alluvial
13
Environmental Earth Sciences (2018) 77:45
(Quaternary) aquifer along this riverine system in Syria,
by using the hydrochemistry, the stable (2H and 18O) and
the radioisotope (3H and 14C) methods, has the following
objectives: (1) to characterize the chemistry of the ER water
and groundwater quality in the alluvial aquifer system, and
their spatial evolutions along the ER pass; (2) to evaluate
the thermodynamic equilibrium conditions controlling the
geochemistry of surface and groundwater resources; (3) to
assess the state of groundwater salinization and detect the
possible salinization sources and related mechanism for the
salinity formation; mostly that developed downstream as
a consequence of intensive irrigation under high evapora-
tion rates; and (4) to definite the origin and renewability of
groundwater in this aquifer system, which helps overall in
defining of suitable management strategies for a better use
of the available groundwater resources, and amelioration of
their quality by adopting appropriate drainage schemes of
no risk on the land fertility in such a dry area and a vital
agronomic sector.
Study area
The study area covers lands generally belong to the ER
basin, located between 34° 30′ and 36° 50′ of latitude N
and 38° 00′ and 40° 55′ of longitude E (Fig. 1). The topog-
raphy of these lands is usually rough. A few small hills can,
however, be seen in the vicinity of the ER banks, mainly
upstream Al-Assad Lake. The elevation of the ER course at
its entrance from Turkey (Jarablous) is ≈ 350 m above sea
level (m a.s.l) and progressively declines in an average slope
of ≈ 0.25 m/km to ≈ 180 m at Albu-Kamal near the Iraqi
border (UNDP-FAO 1966).
The climate of the ER basin is generally semiarid to
arid, with usually a cool (5–10 °C) and rainy winter and a
warm to hot (30–45 °C) summer. As aridity increases from
north to south, the mean annual air temperature (T) raises
from 18 °C (Jarablous) to 20 °C (Albu-Kamal). The value
of mean annual relative air humidity is about 56% in Jara-
blous and decreases to the lowest registered value in the
country (44%) in Albu-Kamal. The cool period is usually
short (Dec. to Jan.), but with the highest relative humid-
ity values (60–70%). During the warmest months (Jul. and
Aug.), this parameter becomes the lowest (25–30%). The
value of potential evapotranspiration varies in the range of
1300–2600 mm, with an average value of 2100 mm. The
rainy season extends between October and May, with a pro-
gressive decrease in the mean annual precipitation amount
from north to south, i.e., from 350 mm in Jarablous to less
than 130 mm in Albu-Kamal (Fig. 1).
The ER, with its long course (entire length,
Lg ≈ 2786 km) and its large basin (total area ≈ 440,000 km2),
is the main fluvial system in the study area. This river, which
Environmental Earth Sciences (2018) 77:45 Page 3 of 18  45

Fig. 1  Location maps of the Euphrates River (ER) basin showing distribution of mean annual precipitation and locations of sampling sites from
wells and the ER water in Syria (adopted from ICARDA 2006 and UN-ESCWA-BGR 2013)

drains lands distributed among five countries (Fig. 1), of In Syria, the ER generally flows inside a depression struc-
which 28% are located in Turkey, 22% in Syria, 47% in Iraq, ture, most probably due to a deep supposed fault, tectoni-
0.03% in Jordan and 2.97% in Saudi Arabia, constitutes with cally known as the “Euphratian Fault System” (Ponikarov
its twin, the Tigris river, the most important rivers in western 1967). Most of the geological formations within this struc-
Asia (ACSAD 2001; UNEP 2001; UN-ESCWA-BGR 2013). ture are placed in the stable section of the Arabian Platform,
Most of the ER flow (88–98%) is originated from the moun- where three main stratigraphical deposits (Paleogene, Neo-
tainous regions in eastern Turkey. The river discharge (Q) at gene and Quaternary) can be distinguished (Fig. 2):
Jarablous varies in the range of 535–1378 m3/s, with an aver-
age value of ≈ 1015 m3/s (UNEP 2001; Işçen et al. 2009). • The Paleogene (Oligocene–Middle Eocene) deposits,
According to a special protocol, Turkey highly controls the mostly outcropped northward in limited areas in the
minimum annual Q value of the ER at ≈ 500 m3/s for both
Syria and Iraq (ACSAD 2001). During the study period,
the average annual Q value of this river was ≈ 686 m3/s at
Jarablous, and ≈ 568 m3/s at Albu-Kamal. A recent analysis
by Trondalen (2009) indicates that the implication of climate
changes within the Middle East region will affect the annual
flow of the ER that will decrease by 29–73%, especially in
the lower part of Syria and Iraq, if no remedial actions are
considered.
The ER in Syria has three main tributaries: Sajor,
Balikh and Khabour (Fig. 1). These tributaries contribute
all together an average Q value of about 60 m3/s. Noting
here that the Khabour river, which is the major tributary
(Lg ≈ 400 km and Q ≈ 50 m3/s), was completely dry during
the period 2000–2006 (Kattan 2001), three dams (Tishreen,
Euphrates and Al-Baath) were also built on the ER course in
Fig. 2  Simplified geological map of eastern Syria showing the dif-
Syria. The Euphrates is the biggest dam that forms the larg- ferent formations along the ER basin from Jarablous to Albu-Kamal.
est reservoir or the so-called Al-Assad Lake (Lg ≈ 75 km). (Adopted from Ponikarov 1967)

13
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vicinity of Jarablous area. These deposits (thickness,
D ≈ 240 m) are generally made up of detritus chalky
limestone at the bottom and massive Nummulitic lime-
stone, with interbeds of marl at the top.
• The Neogene deposits (D ≈ 220 m), largely outcropped
along the ER course. These deposits contain mainly gyp-
sum, sandstone, siltstone, silty clays, clays and pebbles.
• The Quaternary deposits (D ≈ 20 m), largely of alluvial
sediments. These deposits, mostly composed of pebbles,
gravels, loams and sandy loams from Lower to Upper
Quaternary, are widely present in all the terraces devel-
oped across the ER course and its tributaries. The Pleis-
tocene and Recent deposits (D ≤ 0.5 m), mostly made up
of gravels and loams sediments, are also present, with a
thin gypsy–ferrous crust. A few small sheets of volcanic
basalts of the Lower Quaternary also can be recognized
close to Deir-Ezzor area.
From a hydrogeological point of view, several aqui-
fer systems can be distinguished in the ER basin in Syria
(GERSAR-SCET 1977; Khouri 1993; Stadler et al. 2012):
• The Eocene chalky limestone aquifer, largely recognized
near Jarablous.
• The multi-aquifer systems (Cretaceous to Neogene),
mostly widespread downstream Al-Assad Lake and the
edges of the eastern Steppe basin.
• The deep Miocene aquifer, widely present along the ER
course and appears to be unconnected with the upper
alluvial water-bearing system.
• The Miocene–Pliocene water-bearing complex, char-
acterized by the existence of rather fractured (marl and
gypsum) and alluvial formations.
• The Euphrates alluvial aquifer, mostly made up of grav-
els and pebbles of large sizes at the bottom, and loams
and sandy loam sediments of small to fine sizes at the
top, and directly connected with the Miocene–Pliocene
complex.
According to Khouri (1993), the later aquifer is the major
water-bearing system in the ER basin. Due to a rather impor-
tant vertical change in the particle shapes and interspaces
of alluvial materials in this aquifer, a notable difference
exists between the vertical and horizontal permeability val-
ues (GERSAR-SCET 1977). Based on this typical change,
and as a semi-compact to compact sediment layer occurs at
the aquifer bottom, the drainage capacity in the lower part,
composed of fine materials, is less than that in the upper
part. Hence, during the irrigation periods the water amount
vertically penetrated will exceed that flowing horizontally.
This situation causes a successive rising in the groundwater
table, and thus it is very common to observe in many loca-
tions across the ER course that the groundwater table exists
13
Environmental Earth Sciences (2018) 77:45
at a depth between 2 to 4 m below the land surface (Kattan
and Najjar 2005).
Sampling and analytical methods
Groundwater samples were generally collected from ten
wells (G1–G10) that all belong to the Euphrates alluvial
aquifer extending from Jarablous to Albu-Kamal (Fig. 1).
Although a number of groundwater samples (wells Nos. G1,
G2, G3 and G10) were previously collected during 2005
(the CRP Contract No. 12643), the chemical and isotopic
results of these samples are not yet desirably interpreted. A
few supplementary data of groundwater samples collected
from other six wells (G4–G9) were also used in this study,
together with the data of the ER water at three sites (Kattan
2012): (1) its entrance from Turkey (Jarablous), (2) its exit
from Al-Assad Lake (Euphrates dam) and (3) at Deir-Ezzor
station (Fig. 1). Table 1 summarizes the general character-
istics of the sampling sites (geographic coordinates) and
duration of the sampling periods of collected surface and
groundwater samples from the study area.
Collection of surface waters and groundwater samples
was carried out on a monthly basis. All collected samples
were stored in rinsed plastic bottles and preserved in a refrig-
erated room (T below 5 °C) until the time of analysis. A
first one half liter (L) bottle was filled for the determina-
tion of major ions (­ Ca2+, ­Mg2+, ­Na+, ­K+, Cl, S ­ O42− and
−
­NO3 ), for which the related analyses were carried out in
the Geology Department of Atomic Energy Commission of
Syria (AECS), after filtration of the water samples through a
0.45-μm Millipore membrane, using a dual columns instru-
ment (Dionex DX-100), with an analytical error lower than
1 mg/L for each ion. A number of few additional samples of
a 500 mL volume were also collected for analyzing the dis-
solved silica (­ SiO2) content, and the related measurements of
this species were also conducted in the Geology Department
of AECS by using a portable spectrophotometer (Hach) and
specific associated kits.
A second small bottle (50 mL) was filled for analyzing
the stable isotope ratios (δ18O and δ2H), and subsequent
determinations were performed in the Geology Depart-
ment of AECS, by equilibrating a 5 mL of subsample with
small amounts of separate reference gases (­ CO2 and H ­ 2),
and analyzing the resulted gases using a Finnigan Mat
Delta Plus mass spectrometer, with a measurement accu-
racy of ± 0.1 and ± 1.0‰ versus VSMOW for δ18O and
δ2H, respectively. A third bottle of one liter volume was
collected for tritium (3H) measurement, and related analy-
ses were performed after electrolysis, also in the Geology
Department of AECS, using a liquid scintillation counter
(Quantulus 1220), with a measurement accuracy of ± 1
TU. Determinations of radiocarbon (14C) were conducted
Environmental Earth Sciences (2018) 77:45 Page 5 of 18  45

Table 1  General characteristics of the sampling sites (geographic coordinates) and duration of sampling periods of collected riverine and
groundwater samples from the study area
Site no. Location name Sampling period X (Lon. E.) Y (Lat.N.) Altitude Well depth Ground
(ma.s.l.) (m) water depth
(m)

ER1a ER (Jarablous) 2004–2006 38.03000 36.82139 345 – –

ER2 ER (Euphrates dam) 2004–2006 38.55944 35.85694 303 – –
ER3 ER (Deir-Ezzor) 2004–2006 40.15972 35.33694 197 – –
G1 PW (Jarablous) 2005 38.01672 36.81822 350 10 3.7
G2 PW (Al-Mansoura) 2005 38.73175 35.84458 257 15 1.6
G3 DW293 (Al-Mouraieh) 2005 40.21306 35.27556 198 8 2.2
G4 DW157 (Al-Mayadine) 2000–2001 40.316 35.1597 195 10 2.1
G5 DW299 (Al-Mayadine) 2000–2001 40.343 35.15 194 10 2.4
G6 DW443 (Al-Mayadine) 2000–2001 40.374 35.146 194 8 1.9
G7 DW439 (Al-Mayadine) 2000–2001 40.362 35.131 194 12 2.6
G8 PW (Al-Mayadine) 2000–2001 40.491 35.0383 190 15 3.8
G9 PW (Al-Mayadine) 2000–2001 40.466 35.1636 194 12 3.3
G10 DW6 (Al-Ghabra) 2005 40.89500 34.52786 175 12 1.6
a
 Site nos. ER1, ER2 and ER3 refer to the sampling points from the ER at Jarablous, Euphrates Dam and Deir-Ezzor, respectively. Site nos. G1
to G10 represent the groundwater sampling points from the governmental drainage and private wells (DW and PW, respectively) drilled in the
vicinity of the ER in Syria

for a few number of groundwater samples. Collection of Results and discussion

the related total dissolved inorganic carbon (TDIC) was
performed according to the International Atomic Energy
Agency (IAEA) procedures, and the subsequent analyses
of this radioisotope were also carried out in the Geology
Department of AECS by using the same instrument (Quan-
tulus 1220).
The water temperature (T), pH, electrical conductivity
(EC), dissolved oxygen (DO), together with the total alka-
linity (i.e., ­HCO3−) values of all samples were measured in
the field during sampling. T values were measured using
a WTW EC/T meter (cond315i), with a precision of ± 0.2
ºC. The same EC/T meter was also used for the measure-
ment of EC values, with a precision of ± 5 μS/cm. Deter-
minations of pH values were performed using a WTW pH
meter (pH315i), after calibration with two buffer solutions
(pH  =  4 and 7), with a precision of  ±  0.01. Measure-
ments of DO were carried out using a WTW dissolved
oxygen meter (oxi3310) with a precision of ± 0.5%. Total
alkalinity values were determined by a volumetric titra-
tion method (Clark and Fritz 1997), on 100 mL of water
sample, using a WTW pH315i-meter and 1.6 N sulfuric
acid, with a precision of ± 1.5 mg/L.
Quality assurance procedures, according to the ISO/
IEC 17025, are strictly adhered to by all the AECS labo-
ratories. Both the chemical and isotopic analysis results
are periodically verified through the participation in the
different analysis comparison programs of the IAEA and
other local and international organizations.
Chemistry of the ER water
Characterization of the hydrochemical properties of the
ER water in Syria was recently discussed in detail by Kat-
tan (2015). However, it seems useful to report here the
major characteristics (averages and standard deviations)
of the ER water chemistry at Jarablous, the Euphrates dam
and at Deir-Ezzor (Fig. 1 and Table 2). The analytical error
(σ) value of the sampled waters was rather small (< 5%),
indicating thus the goodness of the chemical analysis
results. The chemistry of the ER water shows that the
average pH value for this river slightly fluctuates around
8.3, with a remarkable higher value (8.49) in Al-Assad
Lake, likely because of low dissolved ­CO 2 gas, clearly
identical to that of the atmosphere (log pCO2 = − 3.49).
Similarly, the average concentration of dissolved oxygen
(DO) changes little around 6 mg/L, also with a clear down-
shift in Al-Assad Lake, mostly because of high activity
of microorganisms and aquatic plants living in this lake
(Meybeck 1983).
As it was previously shown by Kattan (2015), the
water quality of the ER in Syria is generally fresh
(TDS  <  0.5  g/L), and with low nitrate concentrations
­(NO3−<5 mg/L). The water quality of this river is slightly
changed since 1976, as the river TDS value at that time
was in the range of 400–700 mg/L (Dosso 1980). In all the

13
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Table 2  Mean chemical composition of water samples collected from the different sites within the study area
Site no. T pH EC SiO2 DO Na+ K+ Mg2+ Ca2+ HCO3− Cl− NO3− SO42 TDS σ

13
(°C) (μS/cm) (mg/L) (%)

ER1 (26)a 13.6 ± 3.2 8.30 ± 0.3 360 ± 26 9.9 ± 1.5 6.6 ± 1.6 15.5 ± 2.2 2.1 ± 0.6 13.7 ± 1.5 34.2 ± 4.5 125.2 ± 18.3 17.4 ± 1.3 2.1 ± 0.6 31.9 ± 2.8 242 ± 20 4.7
Page 6 of 18

ER2 (26) 18.4 ± 6.0 8.49 ± 0.2 403 ± 26.0 6.4 ± 2.3 5.9 ± 1.4 21.2 ± 3.6 2.2 ± 0.5 15.7 ± 1.8 33.9 ± 3.9 118.8 ± 18.0 26.5 ± 3.6 1.9 ± 0.5 51.1 ± 6.1 271 ± 22 2.1
ER3 (26) 18.6 ± 6.3 8.39 ± 0.2 641 ± 123 6.8 ± 2.1 6.1 ± 1.3 39.8 ± 8.5 2.5 ± 0.8 21.2 ± 3.7 49.7 ± 7.5 120.5 ± 17.1 52.9 ± 10.1 3.4 ± 1.0 123.2 ± 33.7 413 ± 61 0.5
G1 (11) 18.8 ± 0.6 7.33 ± 0.1 938 ± 58.0 33.0 ± 1.3 4.98 ± 1.8 28.9 ± 6.4 3.3 ± 2.1 36.2 ± 5.2 80.7 ± 22.4 254.0 ± 45.0 62.5 ± 15.9 72.8 ± 20.2 45.9 ± 10.3 586 ± 84 1.0
G2 (11) 18.5 ± 5.6 7.82 ± 0.3 1065 ± 512 6.6 ± 3.5 5.69 ± 1.8 93.9 ± 113 10.6 ± 12.8 39.1 ± 37 91.7 ± 96.3 125.0 ± 17.5 106.0 ± 126.0 15.6 ± 26.9 401 ± 497 882 ± 908 8.7
G3 (11) 21.7 ± 0.9 7.18 ± 0.1 7520 ± 951 36.3 ± 3.2 3.75 ± 1.0 871.1 ± 246 35.4 ± 39.7 321.8 ± 73 475.5 ± 132 232.2 ± 44.0 969.3 ± 351 39.9 ± 13.7 3649 ± 724 6594 ± 1357 9.6
G4 (1) 22.9 ± 1.3 7.39 ± 0.33 24850 ± 8980 nd 3.98 7664 33.0 744 960 290 6279 nd 8587 24558 10.3
G5 (1) 22.2 ± 0.5 7.53 ± 0.31 23595 ± 9919 nd 5.75 6449 44.4 706 808 233 6871 212 6345 21668 6.6
G6 (1) 21.6 ± 1.1 7.92 ± 0.05 22275 ± 10925 nd 5.44 5546 21.0 848 640 263 6490 nd 5647 19455 5.9
G7 (1) 22.3 ± 0.5 7.32 ± 0.21 37093 ± 12875 nd 5.35 8367 21.0 1280 800 316 9129 199 8700 28811 6.6
G8 (4) 20.8 ± 1.0 7.45 ± 0.15 3838 ± 404 nd 3.86 347 ± 53.7 7.0 ± 1.7 189 ± 17 299 ± 24 374 ± 49.5 475 ± 24.7 6.2 ± 3.2 1281 ± 287 2978 ± 567 0.6
G9 (3) 22.4 ± 2.5 7.11 ± 0.43 5270 ± 1027 nd 6.01 697 ± 52.3 8.4 ± 0.6 312 ± 17 780 ± 0.0 314 ± 45.3 1365 ± 370 13.7 1845 ± 653 5334 ± 298 7.3
G10(8) 20.7 ± 2.2 7.63 ± 0.4 21848 ± 3908 19.2 ± 2.8 4.13 ± 1.4 3267 ± 690 51.2 ± 81.0 830 ± 210 504.8 ± 126 161.9 ± 27.5 6706 ± 1565 43.2 ± 9.0 4918 ± 661 16481 ± 3202 11.3

a
 Number between two brackets indicates the number of analyzed chemical samples; σ means chemical error and nd not determined
2015)

2−
−

− −
2− −

Chemistry of the groundwater
by the following ionic sequences: C

or a ­Na+–SO42− type (Kattan 2015).

and ­H CO 3 type in Jarablous to C

the river water chemistry changes to C

Livingstone (1963) for the same group.
Environmental Earth Sciences (2018) 77:45

it is clearly below the average value (13.1 mg/L) given by

Al-Assad Lake and 9.9 ± 1.5 mg/L at Jarablous. This later

Figure 4 illustrates the temporal variations in TDS values

silica content of the ER ranges between 6.4 ± 2.3 mg/L at
levels at Deir-Ezzor are clearly comparable to those of

G1, G2, G3 and G10 during 2005, with the exception of

­M g 2+, ­K + and ­HCO 3− concentrations, while its salinity

value is extremely close to the average value (10.4 mg/L)

from a ­Ca2+–Mg2+ and ­HCO3− type toward a ­Na+–Cl− type,

clearly demonstrates that the river water chemistry evolves
cases, the average chemical composition of the ER water

of all water samples collected from the ER in Syria (Fig. 3)

­ a 2+–Mg 2+–Na + and
estuary, the water chemistry firstly changes from ­Ca2+–Mg2+
­ a2+ > Mg2+ > Na+ > K+
arid zone rivers, specifically with respect to ­C a 2+, ­Na +
that given for rivers in semiarid zones, mainly in terms of
sitions of the ER water at all monitored sites in Syria (after Kattan

­ a2+–Na+–Mg2+ and
estimated by Meybeck (1983) for the world rivers, while

and ­HCO3  > SO4  > Cl . Then as the ER flows toward its

and ­HCO3− concentrations (Meybeck 1979). The average
composition for this river at Jarablous is fairly similar to
rivers (Meybeck 1979). However, the average chemical
Fig. 3  Piper diagrams showing projections of the chemical compo-

­HCO3−–SO42− type in Al-Assad Lake. Downstream this lake

in the groundwater samples collected from the wells Nos.

­SO4 –HCO3 –Cl type in Deir-Ezzor. The Piper diagram
in Syria is clearly higher than that of the average world

The water chemistry of the ER upstream is characterized

Environmental Earth Sciences (2018) 77:45 Page 7 of 18  45

0.363
0.091
0.113
0.814
0.117
0.826

0.589
SIqua

nd
nd
nd
nd
nd
nd
− 2.297
− 2.126
− 1.664
− 1.935
− 1.063
− 0.025
0.256
0.115
− 0.010
0.137
− 0.423
− 0.057
− 0.103
SIgyp

0.486
0.984
1.011
0.010
0.210
0.428
1.383
1.439
2.276
1.448
1.397
0.982
1.223
SIdol

0.321
0.528
0.556
0.045
0.016
0.149
0.582
0.586
0.917
0.456
0.616
0.531
0.351
SIcal
Fig. 4  Temporal variations of TDS values in groundwater samples

log pCO2

− 3.287
− 3.487
− 3.384
− 1.988
− 2.800
− 1.932
− 2.095
− 2.336
− 2.697
− 2.002
− 2.008
− 1.745
− 2.594
collected from wells Nos. G1, G2, G3 and G10 during 2005

the upstream groundwater in wells Nos. G1 and G2, where

SO4/Cl

1.36
1.44
1.73
0.55
2.73
3.13
1.01
0.68
0.64
0.70
1.99
1.00
0.56
temporal variations in most major ions EC and TDS were
rather small, the temporal changes in these parameters in the
remaining groundwaters were irregular and more elevated,

SO4/HCO3
mainly in ­Na+, ­Cl−, ­SO42− and TDS values. These changes

0.33
0.56
1.32
0.24
4.10

37.62
34.59
27.28
34.97
4.35
7.46
39.79
20.9
could be due to wetting or water recycling related to irriga-
tion water infiltrated toward the groundwater. Table 2 reports
the mean hydrochemical characteristics of the groundwater HCO3/Cl

 Number between two brackets indicates the number of analyzed chemical samples; nd: means not determined
samples collected from all wells (G1–G10) in the study area.
4.21
2.67
1.37
2.61
1.28
0.18
0.03
0.02
0.02
0.02
0.46
0.13
0.01
A relatively high analytical error (σ > 5%) can be observed
for a number of groundwater samples, most probably
Table 3  Mean chemical ratios of water samples collected from the different sites within the study area
Ca/SO4

because some minor elements (i.e., Sr, Ba and B), together

2.61
1.62
1.02
4.28
0.57
0.32
0.27
0.31
0.27
0.22
0.56
1.01
0.25
with a number of some heavy trace metals, were not deter-
mined, although they are all susceptible to be present in such
saline groundwater.
(Ca + Mg)/
(Na + K)

The DO content (3.8–5.7 mg/L) and pH values (7.2–7.8)

of groundwater in all wells were generally lower than those
3.96
3.11
2.40
5.37
1.92
1.39
0.21
0.40
0.23
0.22
0.36
0.45
0.65
of the ER water. The reason for the remarkable decrease in
DO content is likely because of no further oxygen sources

257.0
Na/K

13.5
16.8
28.8
18.0
16.0
82.0
395
247
449
678

141
underground, except that carried by the infiltrated surface 84
water toward the groundwater (Hem 1992). With the excep-
tion of ­HCO3− concentration that ranges from 125 mg/L
Na/Cl

1.38
1.25
1.17
0.73
1.36
1.46
1.88
1.45
1.32
1.41
1.13
0.79
0.76
(well No. G2) to 374 mg/L (well No. G8), the concentrations
of the other major ions, together with TDS and EC values are
Mg/Ca

considerably higher than those of the ER water.

0.67
0.77
0.71
0.80
0.83
1.22
1.28
1.44
2.18
2.64
1.04
0.66
2.72

Although, the average TDS value generally increases from

north to south with river mile, changing from 0.6 ± 0.1 g/L
Ca–Na–Mg/SO4–HCO3–Cl

(well No. G1) to 16.5 ± 3.2 g/L (well No. G10), a few higher

Ca–Mg–Na/HCO3–SO4

TDS values (19.5 < TDS < 28.8 g/L) were observed for

Ca–Na–Mg/Cl–SO4
Ca–Na–Mg/SO4–Cl
Na–Mg-Ca/SO4–Cl

the groundwater in wells Nos. G4–G7, all located at cer-

Ca–Mg/HCO3–Cl

Na–Mg/Cl–SO4

tain distances from the ER course near Al-Mayadine area

Mg–Na–Ca/Cl
Ca–Mg/HCO3

Na–Cl–SO4

(Fig. 1). The relationships between average major ion con-

Na/Cl–SO4
Na/Cl–SO4

Na/Cl–SO4
Water type

centrations and average TDS values (Fig. 5) reveal that the

groundwater salinity downstream is mainly due to three
species ­(Na+, ­Cl− and S­ O42−) that tend to linearly increase
with TDS increasing. The groundwaters most saline are typi-
ER1 (26)a
ER2 (26)
ER3 (26)
G1 (11)
G2 (11)
G3 (11)

G10 (8)
Site no.

cally characterized by a ­Na+ and C ­ l−−SO42− type, with the

G4 (1)
G5 (1)
G6 (1)
G7 (1)
G8 (4)
G9 (3)

following ionic sequences: ­Na  > Ca2+ > Mg2+ > K+ and

+
a

13
45
  Page 8 of 18 Environmental Earth Sciences (2018) 77:45

Fig. 5  Relationships between average major ion concentrations and

average TDS values of groundwaters in all the study wells (G1–G10)
in Syria

­Cl− > SO42− > HCO3−. However, despite ­Cl− is a conserva-

tive ion this species stays rather constant (≈ 6–7 g/L) in
groundwater disposing a TDS value higher than 10 g/L (i.e.,
wells Nos. G4, G5, G6 and G10). Oppositely, the concentra-
tions of the other ions ­(Ca2+, ­Mg2+ and ­HCO3−), which can
participate in the precipitation of carbonate minerals or fixed
in some clay series (Stumm and Morgan 1981), stay rather
low or constant with the increase in TDS values.
The Piper diagram of all groundwater samples collected
from the wells Nos. G1, G2, G3 and G10 (Fig. 6a) helps
to differentiate between the following four water groups:
(1) the groundwater in well No. G1, with a C ­ a2+–Mg2+
and ­HCO3− type, (2) the rather brackish groundwater in
well No. G2, with a C ­ a2+–Mg2+ and ­SO42−–HCO3− type,
(3) the rather brackish groundwater in well No. G3, with a
­Na+–Ca2+–Mg2+ and S ­ O42− type and (4) the saline ground-
water in well No. G10, with a N ­ a+–Cl− type. This diagram
also permits to observe that the groundwater chemistry in the
alluvial aquifer evolves from a ­Ca2+–Mg2+ and ­HCO3− type
toward a ­Na+–Cl− type, rather similar downstream to that
of the seawater.
This chemical evolution is particularly similar to that
obtained on the basis of a modeled thermodynamic simula-
tion essay (Fig. 6b), by adopting progressive evaporation
of a water sample collected from the ER near Deir-Ezzor
(Dosso 1980). The simulation results of this experiment
clearly show that the ER water becomes at a first stage satu-
rated with respect to calcite. Then, as evaporation progresses
the river water becomes in equilibrium with magnesium-
montmorillonite, magnesite ­(MgCO3), gypsum, thenardite
and at a final phase rather saturated with respect to sylvite
(KCl). These results confirm that evaporation is the major
factor that strongly controls the geochemistry of both the ER
Fig. 6  Piper diagrams showing projections of the chemical composi-
tions of the groundwater in wells Nos. G1, G2, G3 and G10 (a), and
the simulated chemical evolution of the ER water during evaporation
(b) (data from Dosso 1980)
water and the groundwater in the adjacent wells along this
riverine system. The low depth of the groundwater table in
this area may favor a fraction of groundwater to move by
capillarity toward the land surface, and then to be evapo-
rated, leaving certain amounts of evaporative soluble salts
(Dosso 1980; Kattan and Najjar 2005). Hence, the sharp
salinization of soil and groundwater, especially developed
in the lower downstream valleys, may be formed by this
flow mechanism.
Ionic ratios of the ER water and groundwater
Calculating the characteristic ionic ratios of the dissolved
major constituents in groundwater, after converting their
concentrations to meq/L, represents a useful indices to
evaluate salinity origin and differentiate between the various
water types (Rosenthal 1987; Hem 1992). Table 3 illustrates
the water types and the calculated mean characteristic ionic

13
Environmental Earth Sciences (2018) 77:45 Page 9 of 18  45

ratios for the ER water at the three mentoring sites and those
for the groundwater in the ten selected wells.
The calculated ionic ratios for the ER water help to dis-
tinguish between: (1) the upstream water, usually character-
ized by high ­Ca2+/SO42− and H ­ CO3−/Cl− ratios, and (2) the
downstream water, gradually of lower values in these ratios.
This distribution in the ionic ratios strongly reflects the car-
bonate character of water mineralization upstream, mainly
in ­Ca2+ and M ­ CO3− species that constitute more
­ g2+ and H
than 60% of the TDS value (Kattan 2015).
With the exception of groundwater in well No. G1, where
­Mg2+/Ca2+ and N ­ a+/Cl− ratios are rather similar to those
of the river, with also identical water types ­(Ca2+–Mg2+
and ­HCO3−–Cl−), the types of groundwater chemistry in
the remaining downstream wells were clearly different,
mainly in terms of ­Ca2+/SO42− and ­HCO3−/Cl− ratios. The
­Na+/Cl− ratio (1.17–1.38) is clearly higher than the range
(0.86–1), reported for common natural waters (Hem 1992).
This ratio suggests therefore a further source of sodium that
most probably comes from the seepage of saline ground-
water into the riverbed (Kattan 2015). Based on ­Cl− mass
balance calculation, Kattan (2008) found that approximately
­ l− flux in the ER water is derived from
one third of the C
the groundwater by drainage return flows in the upstream
areas. However, although the contribution of this drainage
was significantly lower downstream, and as less as 1% at
Albu-Kamal, the remaining two thirds of C ­ l− flux were also
liberated by this component.
The relationship between average N­ a+ and C­ l− concentra-
tions of the ER water and the groundwaters (Fig. 7a) clearly

Fig. 7  Relationships between
average concentrations of ­Na+
and ­Cl− (a), ­Na+ and ­SO42− (b),
­Na+ and ­Cl−+SO24 (c), ­Ca2+
and ­SO42− (d), ­Ca2++Mg2+ and
­HCO3− (e) and ­Ca2++Na+ and
­HCO3− (f) for the ER water
and groundwaters in all the
wells (G1–G10). The line slope
(stoichiometry) is selected to fit
with the ionic ranges calculated
for the different wells

13
45
  Page 10 of 18
shows that the ­Na+/Cl− ratio evolves during salinity increas-
ing from a value of ≈ 0.7 in the ER water at all sites and in
the wells Nos. G1, G2 and G10, to a value of ≈ 1.4 (wells
Nos. G5, G6 and G7), up to a maximum value (1.9) in well
No. G4. Similarly, the relationship between average N ­ a+
2−
and ­SO4 concentrations (Fig. 7b) indicates that the Na/
SO42− ratio evolves from a value of ≈ 0.6 (wells Nos. G2,
G3, G8 and G9), to a value of ≈ 1.4 (well No. G10), up to a
value of ≈ 2 in wells Nos. G4, G5, G6 and G7.
The relationship between average ­ N a + and
− 2−
­Cl +SO4 concentrations (Fig. 7c) shows in the case of
the ER water and brackish groundwaters (wells Nos. G2,
G3, G8, G9 and G10) that one half of the ­Na+ fraction is
linked with both C ­ O42− ions, while in the case of
­ l− and S
most saline groundwaters (wells Nos. G4, G5, G6 and G7)
the ­Na+ fraction clearly becomes much higher (> 80%)..
The relationship between average ­Ca2+ and ­SO42− con-
centrations (Fig. 7d) shows that as salinity increases the
­Ca2+/SO42− ratio becomes lower and less than 0.25 in the
case of the most saline groundwater, specifically in well No.
G7. This ratio is also low (≈ 0.27) in the wells Nos. G3, G4,
G5, G6 and G10, while it is clearly higher (0.6) in well No.
G8. As the mineralization of groundwater in ­Ca2+ and SO24
ions is governed by the chemical equilibrium conditions and
bilateral interactions between the groundwater and the ambi-
­ a2+/SO42− ratio
ent hosting rocks, the one unity value in the C
that characterizes the groundwater in well No. G9 indicates
that all the C­ a2+ and ­SO42− are uniquely coming from dis-
solution of rocks only containing calcium and sulfur, such
as gypsum (­ CaSO4.2H2O) and anhydrite (­ CaSO4). However,
the low ­Ca2+/SO42− ratios (< 0.3), mostly observed in the
saline wells Nos. G3, G4, G5, G6, G7 and G10, prove the
existence of further mineralization sources, mostly with
excess in S­ O42−. This change in the groundwater chemis-
try clearly indicates the effective role of flushing of extra
amount of Na, Cl and S into the groundwater, either from
the rock weathering of drained formations containing gyp-
sum and anhydrite, or from the dissolution of evaporative
soluble salts of no calcium, such as the thenardite ­(Na2SO4),
mirabilite ­(Na2SO4.10H2O) and bloedite ­(Na2MgSO4.4H2O)
minerals, commonly present in abundant amounts on the
land surface in the downstream valleys (Kattan and Najjar
2005). The intense groundwater salinity in well No. 7 is
likely because of the significant evaporation and long dis-
tance from the ER course, i.e., little mixing between the
enriched ambient groundwater and the diluted ER water.
The relationship between average ­C a 2++Mg 2+ and
­HCO3− concentrations (Fig. 7e) shows that the C ­ a2++Mg2+
portion, which usually should be linked with ­HCO3− ion,
is ≈ 2 in the case of the ER water and the groundwater in
well No. G1. This ratio becomes gradually higher with river
mile, ranging between ≈ 5 (wells Nos. G2 and G8), ≈ 13
in wells Nos. G3 and G9, up to a value of 23–35 in the
13
Environmental Earth Sciences (2018) 77:45
most saline wells (G4, G5, G6, G7 and G10). While a value
of ≈ 1–2 in the ­Ca2++Mg2+/HCO3− ratio seems to be typi-
cal for the mineralization of water-draining carbonate rocks
(calcite and dolomite), higher values in this ratio reflect the
influence of further excesses in both ­Ca2+ and ­Mg2+ ions,
likely from the dissolution of non-carbonate materials. This
later case completely corresponds to the case of the saline
groundwater in wells Nos. G4, G5, G6, G7 and G10.
The relationship between average ­C a 2+ +Na + and
­HCO3− concentrations (Fig. 7f) also shows that the ER water
and the groundwater in well No. G1 has a ­Ca2++Na+ frac-
tion two times higher than that of H ­ CO3−. This means that
at least one half of the H −
­ CO3 content is only linked with
­Ca2+ ion, reflecting hence a mineralization type of carbonate
rocks. However, the C ­ a2++Na+/HCO3− ratio that character-
izes the groundwaters in the remaining wells varies from ≈ 5
(wells Nos. G2 and G8) to ≈ 15 (wells Nos. G3 and G9),
up to a range of ≈ 60–80 in wells Nos. G4, G5, G6, G7 and
G10. This later ratio indicates, as well, a further excess in
­Na+ ion, which mostly could be derived from the dissolu-
tion of soluble salts containing sodium, such as thenardite,
mirabilite and bloedite minerals.
Thermodynamic equilibrium conditions
Determination of the thermodynamic equilibrium conditions
of major dissolved constituents present in water forms the
basis for evaluating quantitatively the feasibility of various
possible chemical processes that could occur in natural water
systems. Such studies would help to detect the solubility or
stability of certain minerals susceptible to be formed under
different geological and climatic conditions (Hem 1992).
The software package (WATEQ 4F), developed by Plum-
mer et al. (1976), was used to perform the related calcula-
tions, specially the saturation indexes (SI) with respect to
minerals (Stumm and Morgan 1981), and the speciation of
the principal chemical activities, necessary for studying the
geochemical weathering of silicate minerals (Garrels and
Christ 1965).
Table 3 summarizes the average values of the partial pres-
sure of dissolved C ­ O2, together with the saturation indexes
with respect to calcite, dolomite, gypsum and quartz of the
ER water and the adjacent groundwaters in the different
wells. The obtained results clearly show that the ER water
at all sites is over-saturated with respect to calcite, dolomite
and quartz, and also that the partial pressure values of dis-
solved ­CO2 in the river water ­(10−3.3–10−3.5) are clearly very
close to that of the atmosphere (­ 10−3.5), likely because of the
direct enter connection. Oppositely, the groundwater pCO2
values, ranging from ­10−1.7 to ­10−2.8, are clearly higher than
that of the ER water, likely because of produced ­CO2 gas
within the soil. The groundwaters in all the wells are in equi-
librium or over-saturated with respect to calcite, dolomite
Environmental Earth Sciences (2018) 77:45 Page 11 of 18  45
and quartz. With the exception of wells Nos. G5, G6 and
G8, where the groundwater is impressively over-saturated
with respect to gypsum, the groundwaters in the remaining
wells are under-saturated or close to the equilibrium state
with respect to this mineral.
The activity diagrams related to silicate weathering study
are also used to investigate the controls on aqueous silica and
dissolved major ion concentrations in water with respect to
certain silicate minerals susceptible to be present in nature
(Garrels and Christ 1965). Figure 8 represents plots of the
thermodynamic constraints, specially suggested for testing
the chemical equilibrium reactions between calcium feld-
spars (anorthite) and gibbsite, kaolinite and Ca-montmoril-
lonite (Fig. 8a) and between sodium feldspars (albite) and
gibbsite, kaolinite and Na-montmorillonite (Fig. 8b). Both
diagrams clearly show that the points representing the ER
water are all distributed in the kaolinite stability fields, while
those representing the groundwaters in the different wells
are all regrouped in the stability domains of clay miner-
als, i.e., Ca-montmorillonite, Na-montmorillonite and Mg-
montmorillonite (diagram not shown here). Geochemically,
this distribution proves that after the withering of silicate
rocks (i.e., basalts) the ER water as well as all categories of
groundwater evolve firstly toward equilibrium with amor-
phous silica, quartz and kaolinite. Then as water becomes
more enriched in Ca, Na or Mg ions, the concerned waters
evolve toward equilibrium with the above-mentioned clay
minerals. As the alteration of feldspars commonly occurs in
low rates in most natural conditions, the equilibrium with
respect to gibbsite is still far to be achieved (Wollast and
Mackenzie 1983; Drever 1988).
Assessment of water quality
Analysis of water quality is an important issue in hydro-
chemical studies, mainly for characterizing its suitability for
the various uses. According to recommended standard limits
of the World Health Organization (WHO 2008), the quality
of the ER water in Syria at all sites is generally good and
suitable for drinking water supply. Contrary, the groundwater
Fig. 8  Projections of average
chemical compositions of the
ER water and groundwaters in
all wells in the geochemical
diagrams defining the stabil-
ity fields for calcium feldspars
(anorthite), gibbsite, kaolinite
and Ca-montmorillonite (a) and
stability fields for sodium feld-
spars (albite), gibbsite, kaolinite
and Na-montmorillonite (b) at
25 °C
quality in the different wells, which is unfortunately brack-
ish to saline and with high nitrate concentrations, is thus
harmful and unsuitable for drinking water supply. Suitability
of these waters for irrigation purposes additionally depends
on certain dissolved constituents that affect both the soil
structure (permeability) and plant growth (Singh 2002).
Accordingly, the US Salinity Laboratory Staff has proposed
special specifications for evaluating the suitability of water
quality for irrigation uses (Richard 1954). In view of that a
significant relationship for sodium adsorption ratio (SAR)
was defined, and the SAR value can be computed using the
following equation:
[Na+ ]
SAR = √
(1)
0.5 [Ca2+ ] + [Mg2+ ]
( )
where the ion concentrations [X] are expressed in meq/L.
The calculated SAR values of the ER water at all sites are
generally low (SAR ≤ 2) and gradually increase from ≈ 0.5
(Jarablous) to ≈ 1.6 (Albu-Kamal). This range proves that
the ER water quality is generally suitable for irrigation pur-
poses, and thus its using for lands irrigation will not cause
any permeability problems and swelling of clayey soils types
(Saleh et al. 1999; Singh 2002). Noting that irrigation using
water highly enriched in N ­ a+ enables this ion to be absorbed
by clay particles, and thus displacing ­Mg2+ and ­Ca2+ ions
from the soil. This exchange process results in reducing the
permeability and eventually producing of poor drainage
(Singh 2002).
Figure 9 shows projection of the average SAR values of
the ER water at all sites together with those of the groundwa-
ter in the different wells within the US salinity diagram, in
which the EC parameter was taken as salinity hazard and the
SAR variable as alkalinity hazard. This plot shows that the
ER water upstream and at intermediate sites fall in the C2-S1
field. However, a few water samples, especially those col-
lected from the ER downstream, falls in the C3-S1 field, and
only one sample collected from the ER at Albu-Kamal falls
in the C3-S2 category. This distribution, which indicates a
13
45
  Page 12 of 18 Environmental Earth Sciences (2018) 77:45

48 Stable isotopes of atmospheric precipitation

G4
Sodium adsorption ratio (SAR)
44 G7 and the ER water
40 G5

36 S4
32
G6 The isotopic composition of atmospheric precipitation and
28 the ER water was previously studied in details by Kattan
24
S3
(2012), likely in terms of temporal and spatial variations.
G10
20
Table 4 summarizes the mean isotopic values for δ18O and
16
12
S2 δ2H, together with the corresponding d values, reported for
8 G3 the WR at three sites (ER1, ER2 and ER3) during the period
33 G9
4 S1 3 11 G2
12 12
G8 2004–2006. Figure 10 shows the relationships between the
3
411
3311
88
10
66
210
6
7 10
310
10
8
10
81012
93
10
11
3
93
10
1110
ER3
1010
911
81111
11
10
10
11
1210
9
11
10
11
12
9 3
6
9
10
612
12
10
12
11
9
10
91212
91211
9
10
11 12
12
11
12
11
11
101112
0 858
125ER1*
123 22 1
2
122
52
52
1325
18
5ER25
1 8
4
4
5
56
7
7
4
5
8
4
7
66
5
6
77
5
3
3
33 8386
88
9
8 12
6
9 86 G1
C1 C2 C3 C4 weighted mean δ2H and δ18O values of precipitation at
-4
0.1 1 10 100 five stations in both Syria and Turkey, together with the
EC (mS/cm) δ2H–δ18O relationship of all water samples collected from
the ER system in Syria (Kattan 2015). The equation of the
Fig. 9  Projections of average SAR values of the ER water and least squares regression line fitting the precipitation data is
groundwaters in all wells within the US salinity diagram for classifi- as follows:
cation of irrigation waters. (Adopted from Richard 1954)
𝛿 2 H = (7.52 ± 0.34)𝛿 18 O + (14.73 ± 2.8)
(2)
with R2 = 0.994 and N = 5
medium salinity level and low sodium hazards, implies that
the ER water in Syria can safely be used for irrigation pur- This relationship indicates that the precipitation of the
poses without any danger on soils and plants. In parallel, the studied stations is all situated between the Mediterranean
points representing the groundwater in wells Nos. G1 and Meteoric Water Line (MMWL), defined by Nir (1967) as:
G2 fall in the C3-S1 field. This means that these groundwa- 𝛿 2 H = 8𝛿 18 O + 22 , and the Global Meteoric Water Line
ters are rather good for irrigation uses. However, the remain- (GMWL), given by Craig (1961) as: 𝛿 2 H = 8𝛿 18 O + 10 .
ing groundwaters (wells Nos. G4, G5, G6, G7 and G10) fall Both later equations are rather different from that previously
in the C4-S4 field, indicating hence the absolute hazard of established by Kattan (1997) for the Syrian Meteoric Water
all these groundwaters for irrigation purposes, likely because Line (SMWL) given as:
of the high ­Na+ content.
𝛿 2 H = (8.26 ± 0.37)𝛿 18 O + (19.30 ± 2.7)
(3)
with R2 = 0.963 and N = 9

Table 4  Mean isotopic compositions of water samples collected from the different sites within the study area

Site no.a Number of ana- Location name δ18O δ2H d 3

H 14
C
lyzed samples (‰, VSMOW) (TU) (pmC)

ER1 26 ER (Jarablous) − 8.52 ± 0.2 − 55.1 ± 2.0 13.0 ± 1.0 7.8 ± 0.4 nd

ER2 26 ER (Euphrates Dam) − 7.41 ± 0.2 − 49.1 ± 1.7 10.2 ± 1.1 7.8 ± 0.6 nd
ER3 26 ER (Deir-Ezzor) − 7.24 ± 0.3 − 48.5 ± 1.7 9.4 ± 1.1 7.7 ± 0.4 nd
G1 11 PW (Jarablous) − 6.24 ± 0.2 − 39.0 ± 1.3 10.9 ± 1.2 4.4 ± 0.2 nd
G2 11 PW (Al-Mansoura) − 7.21 ± 0.3 − 48.0 ± 1.8 9.7 ± 1.5 7.5 ± 0.4 nd
G3 11 DW293 (Al-Mouraieh) − 6.50 ± 0.1 − 44.3 ± 0.9 7.7 ± 0.9 8.0 ± 0.5 nd
G4 2 DW157 (Al-Mayadine) − 6.35 ± 0.21 − 49.1 ± 0.9 1.7 ± 0.8 8.5 ± 0.1 nd
G5 3 DW299 (Al-Mayadine) − 6.76 ± 0.09 − 49.1 ± 1.1 5.0 ± 1.2 7.0 ± 0.6 90.91 ± 0.63
G6 2 DW443 (Al-Mayadine) − 7.19 ± 0.06 − 51.6 ± 0.0 5.9 ± 0.6 10.0 ± 2.8 nd
G7 2 DW439 (Al-Mayadine) − 5.93 ± 0.38 − 45.8 ± 2.5 1.6 ± 0.5 4.5 ± 0.1 nd
G8 3 PW (Al-Mayadine) − 7.46 ± 0.18 − 51.6 ± 0.9 8.1 ± 0.8 11.4 ± 0.8 97.02 ± 0.51
G9 2 PW (Al-Mayadine) − 4.53 ± 0.04 − 32.4 ± 0.8 3.8 ± 1.2 5.1 ± 0.5 104.9 ± 0.52
G10 8 DW6 (Al-Ghabra) − 5.95 ± 0.3 − 42.7 ± 1.1 4.9 ± 1.7 7.4 ± 0.5 nd
a
 Site nos. ER1, ER2 and ER3 refer to the sampling points from the ER at Jarablous, Euphrates Dam and Deir-Ezzor, respectively; site nos. G1
to G10 represent the groundwater sampling points from the governmental drainage and private wells (DW and PW, respectively) drilled in the
vicinity of the ER in Syria. nd: means not determined

13
Environmental Earth Sciences (2018) 77:45 Page 13 of 18  45

-20 Stable isotopes in the groundwater

Precipitation stations Antalya 5 4 Adana
-30 Euphrates River Al-Raqqa 2 14
.73 Table 4 compiles the mean isotopic values (δ18O and δ2H),
O+
2.δ
18
3 18 O-8
.5 together with the corresponding d values of groundwater in
-40 Jarablous 7.5 12
48.δ
1 =
δD123 10 3
84 7 12 3
9 3
δD=
5. the study area. With the exception of the groundwater in well
22 8 47411 12110 12
No. G2, where a relatively depleted isotopic composition, simi-
11 11 212 912 11
12
δD ( /00)

49
O+
586455 75
6
48 377
10
88
94
510
10
12
10
11 11
12
3
6610
912
9 95
7811
9 87
6125410
1110
9 6 584
11 11
12499
7
510
1087 12
11
8 5
10
38 11
6
18 4
58
11
10
357
6 96
128
8
11
397
712 5
9675
11
4109
6
87646 4
539 10
6 11 6
-50 .δ
7810
7344
5
11
68
64
46 10
912
512
10
10 97
0
0

=8 +1
34 5E
8

δD
2 21221323223 8 775 6
232113
1
1212111122
2112
2
2 3
7E
111
1221
Diyarbakir 1 =
-60 3
M
W
L 6
Erzurum
M GM
-70
-80
-12 -11 -10 -9
18
δ O ( /00)
Fig. 10  Relationships between weighted mean δ2H and δ18O values
of precipitation at different stations from Syria and Turkey (bleu cir-
cles) and between δ2H and δ18O values of the ER water at all sites in
Syria during the period 2004–2006. (Adopted from Kattan 2012)
The difference between the above two equations is
reflected in the low deuterium excess (d) value, defined
by Dansgaard (1964) as: d = 𝛿D − 8𝛿 18 O . This difference
is basically due to the Turkish rainfalls, likely the Adana
precipitation, characterized by lower d values (d ≤ 16‰).
In all the cases, the observed d values are below the value
(22‰), given for the eastern Mediterranean region. The
line slope value (7.52) is to some extent lower than the
value (8.17), given by Rosanski et  al. (1993) for the
unweighted GMWL, meaning therefore that the rainfalls
were subjected to rather small evaporation (Yurtsever and
Gat 1981).
Similarly, the isotopic composition of the ER water
downstream Al-Assad Lake was more enriched at all sites
with respect to that of the river upstream. According to
the most recent study by Kattan (2015), the sample points
representing all waters collected from this riverine system
in Syria fits nicely a least squares regression line with the
following equation (Fig. 10):
𝛿 2 H = (5.48 ± 0.11)𝛿 18 O − (8.50 ± 0.83)
with R2 = 0.90 and N = 276
The line slope value (5.48) that characterizes the
δ2H–δ18O relationship for this river is clearly lower than
the values 8 and 8.17, respectively, given by Craig (1961)
and Rosanski et  al. (1993) for the GMWL. The slope
value is even lower than the value (7.5), given by Kat-
tan (2012) for the rainfalls in Syria and Turkey. This low
slope means that as the ER water moves toward its estu-
ary is systematically undergone to additional losses by
evaporation, especially in Al-Assad Lake (Kattan 2008).
3
18 O lar to that of the ER water at Jarablous exists, the remaining
8.δ
groundwaters are clearly more enriched compared to Al-Assad
δD
W
L Lake water (δ18O < – 7.4‰ and δ2H < − 49‰), with also
lower d values (10.9‰ > d > 4.4‰) compared to that of the
ER water. Although the well No. G1 is located upstream, its
groundwater is isotopically more enriched compared to those
-8 -7 -6 -5 -4
0
in the further wells downstream. However, the groundwaters in
the wells (Nos. G4, G5, G7), located near Al-Mayadine area,
are all undergone to more intensive evaporation process, mostly
because of the penetration of evaporated saline water, also as
the irrigation of all lands depends on the ER water. Previous
results on the spatial distribution patterns of EC, TDS, δ18O and
d values in Al-Mayadine area (Kattan and Najjar 2005) have
shown a gradual enrichment in the stable isotope compositions
and TDS values, accompanied, in parallel, with a systematic
decrease in the d value with the increasing distance from the ER
course toward the inland. The chemical and isotopic evolution
patterns of groundwater in this part, which could be considered
as the most saline sector in the ER downstream valleys, strongly
indicate the significant role of evaporation and mixing between
the ambient shallow groundwater and the ER water.
The least squares regression line (evaporation line) fitting
the groundwater samples collected from the wells Nos. G1,
G2, G3 and G10 is approximated by the following equation
(Fig. 11a):
𝛿 2 H = (5.77 ± 0.54)𝛿 18 O − (6.02 ± 3.6)
(5)
with R2 = 0.73 and N = 41
The slope value (5.77) is slightly higher than the value
(5.48) given for the evaporation line (Eq. 4) character-
izing the ER water (Kattan 2015). This shift means that
the groundwater in this shallow alluvial aquifer is sys-
tematically subjected to evaporation after the penetration
of recharge water (i.e., irrigation water), but with a less
intensity compared to that affecting the ER water down-
stream. The δ2H–δ18O relationship of groundwater permits(4)
to observe that the groundwater in all the wells is formed
by recharge of evaporated water, entirely taken from the
ER under different air humidity conditions. However,
although the isotopic composition of the groundwater in
well No. G1 is enriched compared to those in wells Nos.
G2 and G3, the line slope value (≈ 7) characterizing this
groundwater clearly indicates that its water is initially
formed from the ER at Jarablous, but under a relatively
more humid condition compared to those prevailing down-
stream (Fig. 11b).

13
45
  Page 14 of 18 Environmental Earth Sciences (2018) 77:45

(a) -30 and thus it has been largely used as a natural radiotracer in
0
Groundwater Evaporation Line -6. many hydrological studies (Eriksson 1983; Yurtsever 1983;
18 O
Well No 7δ 5
= 5.7 -8. Zuber 1994). Table 4 reports the average tritium contents
18 O
G1 δD δ
.48 of the ER water at the three sites, the average tritium con-

L
G1

W
G1 G1
G1 =5

LM
δD
G1G1
G1G1
G1
-40 G1
tents of the groundwater in the different wells, together with
G10
G3 G10 G10
G10
the carbon-14 values of the groundwater in three wells all
73
G1
G3
G10
δD ( /00)

G10
4. G10
+1 G3
G10 G3
G3
G3
G3 G 3
located along this riverine system.
O
G2 G3G3G3 G10
0

18

G3
G2 G2
δ

G2
G2
The average tritium value in the ER water varies little
2
.5

G2G2
=7

G2
δD

G2 G2G2
-50
E
G2
around 7.8 ± 0.6 TU. This content which is significantly
Al-Assad Lake higher than that of the current rainfalls, fluctuating below 6
E
Euphrates River Evaporation Line TU, exceeds even the tritium weighted means (5.5–7.1 TU),
Euphrates River at Jarablous reported by Kattan (2006) for the atmospheric precipitation
-60 during the period 1989–1993. The raison that the ER water
-9 -8 -7 -6 -5 -4
18 0
has a higher tritium content compared to present days rain-
δ O ( /00)
fall is mostly because of the storing of the river water in a
(b) -30 number of dams in both Turkey and Syria. Noting here that
G9 the rainfalls and runoff waters during the 1960’s were more
Well No enriched in tritium content, chiefly because of the earlier
73

.0
-6
4.
+1

18 O nuclear tests (Eriksson 1983). This behavior strongly char-

7δ
O
18

.0
G1 .7
acterizes the ER water that still carries the earlier tritium
δ

-40 +5 =5
52

δD 28
7.

18 O 18 O- enrichment, likely as most of its waters were undergone to

=

δ G10 2δ
δD

0 3.
δD ( /00)

7. G3 δ D=
= certain residence in a number of dam reservoirs.
0

δD G7
L
W

With the exception of the groundwater in wells Nos. G1

LM

G2
R3
R2
-50
G8 G6
R1 Groundwater Evaporation Line
Euphrates River at Jarablous
-60
-9 -8 -7
δ O ( /00)
Fig. 11  Relationships between δ18O and δD values of groundwaters
collected from the wells Nos. G1, G2, G3 and G10 (a) and groundwa-
ters in all the wells (G1–G10) (b)
The groundwaters in the wells (Nos. G2, G3, G9), and
to some extent the well (No. G10), are all derived from an
evaporated ER water. The lower line slope value (≈ 5.8)
means that evaporation occurs under lower air humidity
values, or more aridity conditions compared to that of
Jarablous area. The groundwater in wells Nos. G4–G8 fits
properly a more modified evaporation line, with a lower
slope (≈  3.2). This low slope reflects in fact a higher
evaporation rate, likely because of the pronounced aridity
conditions. The low depth of the groundwater table in all
these wells effectively favors the direct water evaporation
from this shallow aquifer.
Tritium and carbon‑14 in the groundwater
Tritium (half-life = 12.32 years) is the only radioactive envi-
ronmental isotope that constitutes part of the water molecule,
G5 G4
and G7, and to some extent in well No. G9, where the trit-
Al-Assad Lake
ium content was the lowest (3H = 5 ± 0.5 TU), the tritium
content in the groundwater in the remaining wells was in
the range of 7–11.5 TU. The relative increase in the tritium
content in the groundwater downstream is likely because
-6 -5 -4
18 0
of the weak renewability of these resources compared to
those in the wells upstream, or the wells located very close
to the ER course. The strong connection between the ER
water and the shallow ambient groundwaters favors also the
quick mixing between these two water systems, and thus the
faster renewability of groundwater. As tritium can eventu-
ally be used for dating the groundwater age (Mook 2006), a
range of 5 to 15 TU in tritium activity commonly indicates a
modern water recharge of < 5–10 years. Similarly, the high
carbon-14 values in these groundwaters (> 90 pmC) provide
additional strong argument for the quick renewability and the
recent age of all the groundwaters in this aquifer.
Relationships between stable isotopes
and groundwater salinity
Stable isotopes can successfully be used for assessing the
groundwater salinity, detecting its origin, and identifying
the possible mechanism for groundwater contamination
(Carrasco-Cantos 2015). The concept of such approach
basically stands on the idea that when salinity is due to dis-
solution processes or flushing of soluble salts the isotopic
composition of the leaching water would be independent
to any remarkable isotopic changes (Payne et al. 1979).
This means that the isotopic composition of the considered

13
Environmental Earth Sciences (2018) 77:45 Page 15 of 18  45

groundwater will stay rather constant or slightly modi-
fied in function of salinity increasing, likely because of
the low isotopic fractionation (Majoube 1971). However,
groundwater salinity in a similar aquifer may also increase
in function of the path distance or groundwater movement
(Hem 1992). In this case, the major ion concentrations of
the groundwater, as well as the water type, would generally
change, whereas the groundwater isotopic evolution may
occur without any changes, or may be accompanied with
significant modifications in the stable isotope composi-
tion of considered water, mostly because of mixing and
evaporation, depending on the portion of admixed water
members or evaporation rates (Gonfiantini 1986; Kattan
2008). When evaporation is the principal cause for the
groundwater salinity increases, linear relationships would
usually exist between the stable isotope contents and the
conservative ion concentrations (e.g., chloride) of the con-
cerned groundwater.
Figure 12 illustrates the relationships being exist between
the average concentrations of ­Na +, ­C a 2+, ­C l −, ­S O 42−,
­HCO3− and average EC values versus the average δ18O val-
ues. These relationships permit to consider two enrichment
processes for explaining the groundwater salinity increases
in the study area:
1. Enrichment only due to water evaporation. This process
generally affects the groundwaters in wells Nos. G1, G2
and G9, and to some extent those in the wells Nos. G3

Fig. 12  Relationships between
average concentrations of ­Na+
and δ18O (a), ­Cl− and δ18O (b),
­Ca2+ and δ18O (c), ­SO42− and
δ18O (d), ­HCO3− and δ18O (e)
and average EC values versus
average δ18O concentrations (f)
of the ER water and groundwa-
ters in all the wells (G1–G10).
The blue dash lines represent
evolutions related to low and
high salinity increase

13
45
  Page 16 of 18
and G8, for which a rather positive correlation can be
observed between average values in δ18O and above-
mentioned chemical parameters.
2. Enrichment due to a combination of two processes
(evaporation and dissolution). This later mechanism of
enrichment tends to affect principally the groundwater
in wells Nos. G4, G5, G6, G7 and G10, where the TDS
value was much higher than 15 g/L. The salinity origin
of the brackish groundwater in wells Nos. G3 and G8,
where the TDS value was in the range of 3–7 g/L, is also
due to this type of enrichment.
In parallel, mixing between the shallow groundwater with
the ER water may also be considered. The reason for such a
process came from the relatively high tritium levels (8–11
TU) that were recorded in all the wells (Table 4), compared
to that of the ER water (7.7–7.8 TU). Thus, it is notewor-
thy to observe that the degree of water mixing may equally
play an important role in diluting the groundwater salinity.
This trend clearly characterizes the groundwater in the wells
located at a short distance from the ER course, where salin-
ity levels were generally lower than those of wells located
at farther distances from the river course.
Conclusions
The use of hydrochemical and isotopic methods for the char-
acterization of the ER water quality and that of the ground-
water in the Euphrates alluvial (Quaternary) aquifer, largely
widespread along this riverine system in Syria, permits to
extract the following major conclusions:
• The ER water at all monitored sites in Syria is generally
fresh (450 < TDS < 750 mg/L), with a slight increas-
ing in the TDS value with the river mile. As river water
moves from north to south, its chemistry changes from a
­Ca2+–Mg2+ and ­SO42−–HCO3−–Cl− type toward a N ­ a+
− 2−
and ­Cl –SO4 type, mostly because of the saline water
reaching the riverbed, mainly from irrigation return
flows.
• The groundwater quality upstream (well No. G1) is
good and slightly different from that of the ER water at
the matching site. Downstream Deir-Ezzor this quality
becomes largely different from that of the river chem-
istry, primarily because of the drained lands containing
evaporative rocks (gypsum and anhydrite), and dissolu-
tion of soluble salts presumed to be formed by evapora-
tion on the land surface, that later can be transferred
to the aquifer with the penetrated irrigation water. Pat-
terns of the chemical evolution of groundwater quality
clearly prove that evaporation is the main cause for
13
Environmental Earth Sciences (2018) 77:45
the salinity increase in such a dry area. These patterns
highly agree with the simulated thermodynamic chemi-
cal evolution that was obtained based on an experimen-
tal evaporation essay of a water sample from the ER.
• The groundwater salinity is primarily due to N ­ a+, ­Cl−
2−
and ­SO4 species. These ions can largely be liberated
from the dissolution of soluble salt minerals, such
as halite, thenardite, mirabilite and bloedite, vastly
detected in abundant amounts in the upper soil profiles
developed in the downstream valleys. High groundwa-
ter salinity of the wells Nos. G4–G7 is mostly because
of the weak drainage into the river, as these wells are
all rather located far enough from the ER course. The
outcropping of a substratum rich in gypsum close to
this zone may also favor this salinity increasing.
• Although, the groundwater salinity progressively
increases with river mile, according to drained lands,
mostly of a carbonate character upstream, and of rather
fractured evaporative formations (sandy marl and gyp-
sum) downstream, the sharp change in the groundwater
quality between the above two areas is likely the results
of sharp shifts in aridity conditions.
• The stable isotopes (δ18O and δD) permit to differenti-
ate between three evaporation processes: evaporation
under high, intermediate and low humidity conditions.
In parallel, the positive correlations between stable iso-
topes and major ion concentrations can successfully be
used to distinguish between two processes for salin-
ity enrichment, either by evaporation only or by both
evaporation and dissolution.
• High contents in radioisotopes (3H and 14C) indicate
the recent age and quick renewability of groundwater in
the Euphrates alluvial aquifer, and in parallel confirm
that the water origin is fully belonged to the ER water,
either by direct bilateral connection or by vertical infil-
tration of irrigation water, totally taken from the ER.
• The recommended scheme for decreasing the saliniza-
tion of soil and groundwater along this riverine sys-
tem is preferably the continuous drainage of the saline
groundwaters into the riverbed. Increasing of the num-
ber of drainage wells and their discharges may also
facilitate the lowering of the shallow groundwater table
to certain depths, and thus eliminating the capillary
water movement.
Acknowledgements  The author acknowledges particularly Prof. I. Oth-
man, Director General of AECS, for his support and encouragement.
The IAEA Organization, in particular, Mrs. P. K. Aggarwal and M.
Choudhry are deeply acknowledged for their assistance. The author is
also grateful to Prof. W. Rasoul Agha for his valuable remarks. Thanks
are also due to the technical staff of the Geology Department at AECS
who contributed to this work.
Environmental Earth Sciences (2018) 77:45 Page 17 of 18  45

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