You are on page 1of 11

Journal of African Earth Sciences 134 (2017) 230e240

Contents lists available at ScienceDirect

Journal of African Earth Sciences

journal homepage:

Assessment of hydrogeochemistry and environmental isotopes of

surface and groundwaters in the Ktahya Plain, Turkey
Berihu Abadi Berhe a, *, 1, Ug
ur Erdem Dokuz b, Mehmet elik c
Ankara University, Graduate School of Applied Science, Geological Engineering Dept., 06100, Tandogan, Ankara, Turkey
Omer de, Turkey
Halisdemir University, Faculty of Engineering, Geological Engineering Dept., 51240, Nig
c lbas, Ankara, Turkey
Ankara University, Faculty of Engineering, Geological Engineering Dept., 50th Year Campus, 06830, Go

a r t i c l e i n f o a b s t r a c t

Article history: The aim of the present work is to determine the geochemical processes that control the nature of the
Received 31 January 2017 groundwater and assess the quality of water for drinking and public health purposes. Surface and
Received in revised form groundwater samples of Ktahya plain were analyzed for their physio-chemical and environmental
20 May 2017
isotope properties. The relative concentrations of the water ions were found to occur in the order of
Accepted 22 June 2017
Available online 22 June 2017
Ca2>Mg2>(K Na) and HCO 2- 
3 >SO4 >Cl . Piper diagram shows that Ca-Mg/Mg-Ca-HCO3 was the
dominant water types. Waters in the area were super-saturated with respect to carbonates. However,
they were under-saturated with respect to sulphate minerals. The groundwaters had a mean isotopic
composition of 67.32 d2H and 9.72 d18O and were comparatively lower than surface waters 64.64
Water quality d2H and 9.25 d18O. Tritium activities in groundwater from the wells ranged from 1.00 to 8.38 TU with a
Water types mean value of 4.37 TU. The impact of agricultural practices and poor sanitation conditions is indicated by
Isotopes the positive correlation between K - NO   
3 , K - NO2 and HCO3 - Cl ions as well as Na and Mg
Geochemical evolution with SO2
4 ion. The groundwater quality of Ktahya plain is inuenced by various natural and anthro-
Ktahya plain pogenic factors.
2017 Elsevier Ltd. All rights reserved.

1. Introduction upstream of Porsuk dam the water of which is used by people living
in Eskisehir and Ktahya for both irrigation and domestic purposes.
Groundwater is one of the most crucial resources for human life. Heavy metal concentrations in soil samples and leaves of trees and
The quality of water depends upon the geological environment, herbaceous plants in Ko pro
ren basin have relatively higher con-
natural movement and human activities. Nowadays, basic demands centrations (Ark and Yaldz, 2010).The waters form spring, rivers
for fresh water are for the purpose of irrigation, household and and groundwaters of Ktahya plain contain As, Pb, and U concen-
municipal water use, and industrial uses (UNEP/WHO, 1996). trations and the As concentration in all waters is above the
The present study area, Ktahya plain and its catchment lies maximum contaminant level (Kavaf and Nalbantcilar, 2007). In the
between 225000 and 268000E longitude and 4345000e4380000N study area, people of this district and surrounding villages are the
latitude with an area of around 93 km2 and its total catchment primary users of groundwater for drinking, industrial and irrigation
covers about 550 km2. It is crossed by two perennial rivers called and the surface water irrigation for purposes.
the Felent and the Porsuk Rivers (Fig. 1). According to the data The area is one of the Turkey's regions experiencing an expo-
recorded at Ktahya Meteorological Station between the years 1975 nential growth of intensive agriculture and industrial activity. The
and 2011, the mean annual precipitation and air temperature are interactions between agricultural irrigation, surface water and
543.85 mm and 10.81  C, respectively. groundwater resources are always very close. The agricultural ac-
The study area is located in downstream of Ko ren plain and tivities and industrial establishments in Ktahya city such as sugar
factories, nitrogen and magnesium factories and leather industries
are responsible for disposing of treated and untreated efuents in
the natural drainage system of the Felent and the Porsuk rivers.
* Corresponding author.
E-mail address: (B. Abadi Berhe). The most common nitrogen fertilizer currently used in all the
Wollo University, College of Natural Science, Department of Geology, 1145, agricultural lands of the Ktahya plain are urea (CO(NH2)2), DAP
Dessie, Ethiopia.
1464-343X/ 2017 Elsevier Ltd. All rights reserved.
B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240 231

conductivity and transmissivity was 0.11 m/day and 8.59 m2/day,

respectively. Limestone is the water-bearing lithology of the Emet
Formation. The overall yield of aquifer constants is generally high
compared to other aquifers of the study area. In this aquifer, there is
a well with a capacity of about 84.27 L/sec. The mean values of
hydraulic conductivity and transmissivity of limestone aquifer were
2.80 m/day and 350.81 m2/day, respectively (Berhe et al., 2014). The
depth to groundwater level of some wells in alluvial aquifer was
measured in June 2014; and its water table contour map was given
in Fig. 2. According to Figs. 2 and 3, the alluvial aquifer feeds the
surface water of the study area.

3. Materials and methods

To determine the nature of water chemistry and rock-water

interaction, 21 groundwater and 6 surface water samples were
collected during the period of December 2013 from the study area.
During the same time, 15 groundwater and 4 surface water samples
were collected for d2H - d18O and 15 groundwater samples were
collected for tritium concentration analysis. Physical properties of
water measurements like temperature and pH were carried out in
the eld using standard eld equipment (Multi 350i multi-
Water samples were ltered using 0.45-mm disposable capsule
lter for major cation and anion analysis. All samples were
collected as 1 L for tritium and 250 ml for all others analyses in
plastic polyethylene bottles with tightly tting covers. The analysis
Fig. 1. Location of study area and sampling points. was done using DIONEX LC25, ICS-1000 High-Performance Ion
Chromatography system, YSI MPS 556 Multi-probe system, and
Automatic acid titration burette (for HCO 2-
3 and CO3 ) at Hacettepe
((NH4)2HPO4), ammonium sulphate ((NH4)2SO4), ammonium ni- University Water Chemistry Laboratory in Ankara, Turkey. The
trate (NH4NO3), magnesium sulphate (MgSO4), potassium nitrate American Public Health Association (APHA, 1989) standard
(KNO3) and potassium sulphate (K2SO4) (KSM, 2012). Methods were used for the Examination of Water and Wastewater.
Hydrogeochemical processes such as dissolution, precipitation, The stable isotopic analyses were performed at the Laboratory of the
ion exchange and the residence time along the ow path govern international research and application center for karst water re-
chemical compositions of groundwater (Martinez and Bocanegra, sources in Hacettepe University, Ankara, Turkey (Berhe et al., 2014).
2002). The main objective of the present work is to investigate The hydrochemical results were plotted on Piper diagram using
the geochemical processes that control the nature of the ground- AquaChem 5.1 software. Statistical descriptive analysis and corre-
water and assess the quality of water for drinking and public health lation between different parameters of waters were done by SPSS
purposes. The study was performed using hydrochemical and software package version 16.0. Mineral saturation index of all water
environmental isotopic data of oxygen-18, deuterium and tritium. samples was calculated using PHREEQC Interactive 2.12.4 program.

2. Geology and hydrogeology 4. Hydrogeochemistry

The major lithological formations of the area include the The physicochemical parameters of surface water samples
Sarcasu Formation, Arkaya Formation, g rler Complexes, Sab- collected from the Felent and Porsuk Rivers and groundwaters in
uncupnar Formation, Emet Formation, Parmako ren Formation December 2013 were compiled in Table 1. The average water tem-
and Alluvials (Fig. 2). The basement rocks are comprised of meta- perature, pH and electrical conductivity values of the surface wa-
morphic schists, Marbles and o g
rler Complexes rocks (DSI, 1981; ters were 13.2  C, 8.43 and 907.25 mS/cm whereas groundwater

DSI, 2003; Ozburan, 2009). samples had 13.21  C, 8.18 and 1006.90 mS/cm, respectively. The pH
Sarcasu Formation of Paleozoic age is composed of schists, calc- values of all waters used in the study area elaborate a trend of
schist, quartz schist and crystallized limestone and overlain by alkaline chemical reaction within the groundwater system (Tables 1
Arkaya Formation of Upper Permian-Lower Triassic age, Marble. and 2).
Crystalline limestones unconformably overlie the ayca Tuf and at Minimum, maximum and mean concentrations of ions present
the top, and it is unconformably covered by Pleistocene age of in surface and groundwater from the study area are presented in
Parmako ren Formation and alluvials. The Quaternary alluvial, Tables 1 and 2. The relative concentrations of the surface and
which covers the plain, comprises uviatile pebble, gravel, sand, groundwater ions occur in the order of Ca2>Mg2>(K Na) and
and silt, is widely distributed in this plain, and has a maximum HCO 2- 
3 >SO4 >Cl . The predominant cations of surface waters were
depth of 100 m. Ca2 and Mg2 with a mean value of ion concentration 96.42 and
The gravely and sandy horizons in Ktahya plain form one of the 38.68 mg/l, respectively, whereas HCO 3 with a mean value of
best aquifers. The mean hydraulic conductivity (K) and trans- 441.21 mg/l was a dominant anion. Among the major cations of
missivity (T) obtained from analysis of pumping test and recovery groundwater of the plain same as surface waters Ca2 and Mg2
data for this aquifer were 44.42 m/day and 213.48 m2/day, were again predominates and their average concentration were
respectively. The sandstone and gravelstone of Parmako ren For- 92.57 and 52.82 mg/l respectively. Among the major anions, HCO 3
mation are permeable material and its mean value of hydraulic with an average concentration of 414.45 mg/l was the dominant ion
232 B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240

Fig. 2. Geological map of the study area (modied from DSI, 1981; 2003; Ozburan, 2009).

(Tables 1 and 2, and Fig. 4). compared to Ca2 and Mg2 ions, 3 water samples were found out
above allowable TSE-266 limits. Nevertheless, none of them were
above WHO limits (Table 2).
5. Hydrochemical facies
The nitrate concentration value obtained from two water sam-
ples was higher than that of TSE-266 and WHO limits for drinking
Piper diagram is the most convenient way for plotting the re-
water. The results of nitrite concentration of study area depict that
sults of multiple analyses on the same graph, which may disclose
4 water samples exceeded the allowable limits of TSE-266. How-
grouping of certain samples and show different hydrochemical
ever, comparing with permissible limits of WHO all water samples
facies or origin of groundwater (Piper, 1944). By using the Piper
are under the limits. NH4 concentration of water samples disclosed
diagram, the surface and groundwaters of the study area can be
that about 33.3% and 4.7% were above the permissible limits of TSE-
categorized into the following groups: Ca-Mg-HCO3 (66.67%), Mg-
266 and WHO, respectively (Table 2). The concentration of SO2- 4 in
Ca-HCO3 (18.52%), Ca-HCO3 (7.41%), Mg-Ca-SO4-HCO3 (3.7%) and
groundwater reveals that only one water sample exceeded the
Mg-Ca-HCO3-SO4 (3.7%), revealing that the Ca-Mg-HCO3 water type
standard allowable limits of TSE-266 and WHO for SO2- 4 (Table 2).
followed by Mg-Ca-HCO3 was the most dominant type in the study
area (Fig. 4a). According to Fig. 4b, we can observe that both surface
and groundwaters are plotted in the same area indicating that they 7. Composition diagrams
are from the same origin.
The most acceptable method to classify and compare inter-
mixing fresh and saline waters based on ionic composition is by
6. Drinking water quality
plotting the chemical data on a composition diagrams. Mixing lines
indicate the mix of contaminated and fresh end members in various
The analytical physio-chemical parameters of groundwater
proportions (Mazor, 2004). The surface and groundwaters vary
were compared with the standard guideline values as recom-
notably in their chemical concentrations, the data plot on straight
mended by the Turkish Standards Institution (TSE-266, 2005) and
lines is an indication for a positive correlation between Ca2, Mg2,
World Health Organization (WHO, 2008) for drinking and public
Na, HCO 2- 
3 , SO4 and Cl with the total dissolved ion (TDI) (Fig. 5).
health purposes (Table 2).
Fig. 5a and d shows that the line extrapolating to values on the Ca2
Temperature, pH (except 3 samples according to WHO), and the
and HCO 3 axis indicates that both intermixing waters contain a
concentration of ions, such as Na, Ca2, PO3-  
4 , F and Cl in the
signicant concentration of Ca2 and HCO 3 . In Fig. 5b, c, e and f, the
investigated groundwater samples were within the maximum
line extrapolates to point in the TDI line, showing the fresh end
permissible limits TSE-266 and WHO standards. Only one of the
member contains a signicant concentration of ions other than
groundwater samples exceeded the EC limit of TSE-266 standard,
Mg2, Na, SO2- 
4 and Cl .
but two samples according to WHO. Furthermore, 23.8% of the
samples exceeded the hardness permissible limit of WHO. The
concentration of Mg2 shows that 28.3% and 4.7% of the samples 8. Correlation coefcient analysis
exceeded the acceptable limits of TSE-266 and WHO, respectively.
Although K concentration of the groundwater is very low as The correlation coefcient is a vital method in building the
B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240 233

Fig. 3. Hydrogeological cross sections. Lines of section indicated on Fig. 2.

relationship between two variables (Anandakumar et al., 2009). well as Na and Mg2 ions with SO2- 4 ion, indicating the anthro-
Pairs that have high positive correlation show the dependency of pogenic impact from agricultural practices and poor sanitation
one parameter on the other (Sharma and Sharma, 2011). conditions. Other moderately inter-relationships exist as shown in
Correlations between major ions in surface and groundwater Table 3.
within the study area were carried out using Pearson's correlation
analysis in SPSS 16.0 program (Table 3). Correlation coefcients of
9. Molar ratio between major ions
major and some minor ions were computed using values of con-
centrations of the different ions in mg/l. The high correlation co-
Na/Cl relations: When halite dissolution is accountable for
efcient between Na- Cl, Mg2 - HCO 2 
3 and Ca - HCO3 ions was
sodium, the Na/Cl molar ratio is nearly one, whereas a ratio >1, it
observed. Therefore, it can be concluded that for most of the water
is typically deduced that Na is released from a silicate weathering
samples of the area Na and Cl, Mg2 and HCO 3 , Ca
and HCO
reaction (Meybeck, 1987). In the current study area, Na/Cl molar
have originated from the common source. Perfect correlation be-
ratio generally ranges from 0.69 to 6.36 with an average of 1.78. In a
tween EC and major ions (Ca2, Mg2, Na, HCO  2-
3 , Cl and SO4 )
plot of Na against Cl (Fig. 6), most of the samples lie above 1:1
indicates that EC is a measure of major ion concentration in water
trend line showing excess Na. This excess Na may be the result of
silicate weathering reaction process or anthropogenic activities.
There is a very high positive correlation between K- NO 3
Ca2/Mg2 relations: In the study area, the dominant cations
(r 0.97), K- NO
2 2   2
2 (r 0.84) and HCO3 Cl (r 0.83) ions as
were calcium and magnesium, while bicarbonate was dominant
234 B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240

Table 1 et al., 1998; Elango et al., 2003).

Statistical descriptive of physicochemical of surface waters (n 6) of the study area. In the study area, the Ca2/Mg2 ratio of the surface and
Parameters Units Min Max Mean groundwater samples ranged between 0.25 and 12.86 and its mean
Ph e 7.70 9.67 8.43 0.74
value was 1.88 (Fig. 7). About 77.8% samples had a ratio <2
C 10.30 15.20 13.20 1.89 disclosing the dissolution of calcite, whereas the rest 22.2% samples
EC mS/cm 613 1111 907.25 231.92 had a ratio >2, which indicates the effect of silicate minerals.
Li mg/l 0.00 0.02 0.01 0.01 (Ca2 Mg2)/HCO 2
3 relations: Appraisal of the slopes of Ca
NH 4 mg/l 0.00 13.14 2.77 5.23 2 
and Mg versus HCO3 gives crucial information about the sources
K mg/l 2.61 30.51 9.19 10.59
mg/l 9.74 31.97 22.05 9.78 of Ca2 and Mg2 in groundwater (Richter and Kreitler, 1993).
Mg2 mg/l 21.32 63.95 38.68 19.05 Dissolution of silicate and oxidation of organic matter may have
Ca2 mg/l 81.02 119.66 96.42 15.59 produced the excess HCO3- in the groundwater (Seleem, 2014).
PO3- mg/l 0.00 0.69 0.23 0.27
4 In the study area, a plot of Ca2 Mg2 versus HCO3 shows that
Br mg/l 0.02 0.17 0.07 0.05
mg/l 0.08 0.31 0.21 0.08
about 96.2% of sampled waters plot below the 1:1 aquiline (Fig. 8).
NO 2 mg/l 0.17 1.31 0.50 0.43 This indicates a deciency of Ca2 Mg2 relative to HCO3-.
NO 3 mg/l 0.19 19.9 6.01 7.51 Therefore, some HCO 3 is also coming from processes other than
Cl mg/l 2.36 31.4 19.65 12.1 calcite or dolomite dissolution, or the Ca2 and Mg2 are lost in the
cation exchange reactions and it might have been balanced by Na
4 mg/l 9.05 90.03 42.73 33.42
HCO mg/l 337.57 574.47 441.21 86.94
and K or supplied by silicate weathering.
TDI meq/l 12.26 22.22 18.15 4.64

Table 2
Statistical descriptive of physicochemical of groundwaters in the study area and comparing with standard drinking water quality limits, TSE-266 (2005) and WHO (2008).

Parameters Units Groundwater (n 21) TSE (266) WHO

2005 (2008)

Min Max Mean Maximum permissible No. of samples > standard limit Maximum permissible No. of samples > standard limit

Ph e 7.49 9.11 8.18 0.43 6.5e9.2 None 6.5e8.5 3

T C 8.50 17.1 13.21 1.78 25 None 30 None
EC mS/cm 483.00 3135 1006.9 647.11 2000 2 1500 2
Hardness mg/l 239.16 1363.09 448.23 251.13 e e 500 5
Li mg/l 0.00 0.09 0.02 0.02 e e e e
NH 4 mg/l 0.00 3.10 0.61 0.72 0.05e0.5 7 1.5 1
K mg/l 0.60 158.99 17.18 42.69 12 3 50 None
Na mg/l 2.27 105.54 22.59 27.12 175 None 200 None
Mg2 mg/l 6.89 237.91 52.82 48.56 50 5 150 1
Ca2 mg/l 21.93 154.3 92.57 35.45 200 None 250 None
PO3-4 mg/l 0.00 1.39 0.23 0.37 5 None 6.5 None
Br mg/l 0.00 0.47 0.09 0.11 e e e e

F mg/l 0.00 0.43 0.21 0.13 1.5 None 1.5 None
NO 2 mg/l 0.11 2.94 0.48 0.63 0.1 16 3 None
NO 3 mg/l 0.07 225.43 28.35 57.45 50 2 50 2
Cl mg/l 1.78 173.94 29.62 42.79 600 None 250 None
SO4 mg/l 2.73 649.43 76.91 142.7 250 1 250 1
HCO 3 mg/l 275.39 731.41 414.45 119.22 e e e e
TDI meq/l 9.67 62.70 20.14 12.94

10. Hardness

Hardness is a term relating to the concentrations of certain

metallic ions, predominantly magnesium and calcium in the water.
It is usually expressed as an equivalent concentration of dissolved
calcite CaCO3. Water hardness usually expressed as total hardness
(TH) is given by eq (1).

TH 2:5 Ca2 4:1 Mg2 (1)

Where TH, Ca2 and Mg2concentrations are all in mg/l (Todd,

Fig. 4. Piper diagrams of surface and groundwaters in Ktahya Plain. In the study area, the total hardness varies from 239.16 to
1363.09 mg/l with a mean value of 437.88. According to Freeze and
Cherry (1979) classication, 18.5% of the water samples are hard,
anion in groundwater. The points plotted on the line Ca2/Mg2 1 while 81.5% falls under very hard category (Tables 4 and 5).
indicate waters controlled by dolomite dissolution while the Ca2/
Mg2 ratio ranging from 1 to 2 characterizes the dissolution of
11. Ion exchange
calcite (Maya and Loucks, 1995). In natural waters, Ca2/Mg2 ratio
greater than 2 is mainly due to the dissolution of silicate minerals,
Chloro Alkaline Indices (CAI): Schoeller (1967) has formulated a
which contribute calcium and magnesium in groundwater (Katz
formula used to be known as the ion exchange between the
B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240 235

12. Saturation index (SI)

The saturation indices quantitatively describe the deviation of

water from equilibrium with respect to dissolved minerals (Jalali,
2010). The saturation index (SI) for a particular mineral generally
shows whether the groundwater is at equilibrium (SI 0), under-
saturated (SI < 0) or super-saturated (SI > 0) with respect to that
particular mineral.
In the study area, both surface and groundwater samples were
saturated with respect to calcite, aragonite and dolomite disclosing
that precipitation takes place, whereas samples were under-
saturated with respect to sulphate minerals (anhydrite and gyp-
sum) (Table 5). Therefore, water chemistry in the study area was
largely affected by the dissolution of carbonate minerals.

13. Environmental isotope studies

13.1. Stable isotopes

On the basis of large numbers of meteoric water collected at

different latitudes, it has been shown that d18O and d2H values of
Global Meteoric Water Line (GMWL) are linearly related as repre-
Fig. 5. A composition diagram of surface and groundwater of Ktahya Plain. Concen- sented by the equation: d2H 8d18O 10 (Craig, 1961). Moreover,
trations are given in meq/l. the Local Meteoric Line established for Isparta (ILMWL) is

Table 3
Correlation coefcients between major ions in surface and groundwaters of study area.

Parameter pH EC Li NH
4 K Na Mg2 Ca2 PO3-
4 Br F NO
2 NO
3 Cl SO2-

pH 1
EC 0.28 1
Li 0.08 0.45 1
NH 4 0.23 0.10 0.04 1
K 0.11 0.55 0.87 0.08 1

Na 0.27 0.96 0.54 0.22 0.59 1
Mg2 0.31 0.92 0.22 0.06 0.32 0.85 1
Ca2 0.15 0.71 0.36 0.02 0.41 0.66 0.43 1
PO3-4 0.07 0.26 0.78 0.12 0.62 0.30 0.07 0.25 1
Br 0.29 0.93 0.36 0.13 0.41 0.93 0.88 0.62 0.16 1
F 0.27 0.53 0.45 0.14 0.32 0.64 0.49 0.27 0.36 0.62 1
NO 2 0.07 0.50 0.68 0.18 0.84 0.47 0.33 0.37 0.49 0.26 0.21 1
NO 3 0.12 0.49 0.84 0.16 0.97 0.51 0.27 0.36 0.59 0.31 0.26 0.84 1

Cl 0.29 0.99 0.44 0.13 0.52 0.97 0.92 0.65 0.21 0.95 0.56 0.45 0.47 1
SO4 0.33 0.92 0.22 0.12 0.24 0.89 0.95 0.57 0.05 0.92 0.52 0.21 0.19 0.94 1
HCO 3 0.16 0.90 0.39 0.19 0.55 0.83 0.76 0.79 0.31 0.79 0.42 0.54 0.45 0.83 0.72 1

Strong correlations between two parameters are showed in bold numbers.

groundwater and its surroundings during residence or travelling in 2005). Variations in the
d2H 8d18O 12.16 (Sayn and EypogluO,
the aquifer (eq (2) and (3)). Positive CAI indicates the exchange of stable-isotope signature of groundwater are due to natural varia-
Na and K from the water with Mg2 and Ca2 of the rocks and is tions in the isotopic composition of rainfall such as mixing with
negative when there is an exchange of Mg2 and Ca2 of the water pre-existing waters, and evaporation during percolation through
with Na and K of the rocks (Nagaraju et al., 2006; elik et al., the soil and/or the unsaturated zone (Kendall and McDonnell,
2008). 1998).
 19 water samples for stable isotope analyses (oxygen and
Cl  Na K hydrogen isotopes) were collected during December 2013 from
CAI1 (2)
Cl surface water, shallow and deep groundwater through December
2013 (Table 6) and were plotted as can be seen in Fig. 9. The

Cl  Na K measured d2H and d18O values of surface water samples collected
CAI2 (3) during this study range from 67.54 to 61.50 and 9.80 to 8.25,
3 CO3 NO3
4 respectively. On the other hand, groundwaters range from 72.23
According to Table 5, 92.6% of the samples from the study area to 61.27 and from 10.45 to 8.43, respectively. The result is
showed negative ratios indicating an indirect base-exchange reac- disclosing that the surface and groundwaters are isotopically
tion. During this process, the host rocks were not considered to be depleted (Table 6). The groundwaters have a mean isotopic
the principal sources of dissolved solids in the water and reected composition of 67.32 (d2H) and 9.72 (d18O) and these values are
the dominance of direct ion-exchange of Na/K in the water with comparatively lower than surface waters 64.64 (d2H) and 9.25
Mg2/Ca2 in the host rock. (d18O), thus surface waters are more positive than groundwaters
236 B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240

Na+ (mmol)

l ine
3 1:1

0 1 2 3 4 5 6
Cl- (mmol)

Fig. 6. Na versus Clgraph.

Table 4
Hardness of waters.

Hardness Water classication % Result of this study

0e75 Soft e
75e150 Moderately hard e
150e300 Hard 18.5
>300 Very hard 81.5

meteoric origin and implying that modern rainfall is the dominant

component of such groundwaters. The groundwater is plotted far
below the meteoric water lines, proposing that they have under-
gone some evaporation before or during their underground trans-
portation system (Fig. 9).
Clark and Fritz (1997) established d18O-Cl- relationship graph
Fig. 7. Ca2/Mg2 ratio graph of water samples. that helps to assure the importance of evaporation and dissolution
of evaporates. However, in the diagram of d18O against Cl ions, the
correlation between d18O and Cl ions of groundwater is very poor
(R2 0.076) (Fig. 10). This implies that even if evaporation occurs,
its impact upon the salinization of groundwater may be

13.2. Tritium

Tritium, with its half-life of 12.23 years, has been widely used for
the approximation of recent subsurface water residence time
(Lucas and Unterweger, 2000). In some cases, research workers
estimated the age of groundwater from tritium concentrations
(Weissmann et al., 2002; Craig and Johnson, 2008; LaBolle et al.,
2006; Cook and Herczeg, 1998).
To distinguish the water that was recharged relatively recently
from older water, samples were analyzed for tritium content.
Fig. 8. Ca2 Mg2 against HCO
3 graph.
Tritium concentration in groundwater from the wells of the study
area in December 2013 ranged from 1.00 to 8.38 with a mean value
revealing evaporation effect on surface waters. However, they are of 4.37 TU (Table 6).
generally similar and are plotted on the same area on d2H - d18O, The tritium contents in shallow groundwater ranged from 2.52
indicating that they have originated from the same source, which to 8.38 TU. However, the deep groundwater samples taken from
sample numbers PO-1 and K-1 had 1 and 1.66 TU, respectively,
supports the Piper graph.
The diagram d2H - d18O shows that the surface and groundwater indicating the presence of relatively old groundwater in this part
plot on/or is close those of ILMWL and the GMWL suggesting their (Fig. 11a).
The graph of tritium content of groundwater and its measured
B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240 237

Table 5
Statistical descriptive of Saturation Indices (SI), Total Hardness (TH, mg/l) and Chloro Alkaline Indices (CAI, meq/l) of surface and groundwater in the study area.

Sample No SIcalcite SIaragonite SIdolomite SIgypsum SIanhydrite TH CAI1 CAI2

Surface waters (n 6) P-3 1.09 0.94 1.78 2.58 2.83 295.49 6.37 0.07
PP 1.38 1.23 2.37 2.17 2.42 306.52 1.78 0.05
P 0.67 0.51 1.03 2.09 2.34 316.37 1.48 0.12
F-1 2.24 2.08 4.44 1.77 2.03 510.03 0.50 0.04
F-2 1.62 1.46 3.17 1.63 1.89 519.3 0.37 0.03
F-3 0.94 0.79 1.61 2.15 2.40 462.33 1.89 0.14
Min 0.67 0.51 1.03 2.58 2.83 295.49 6.37 0.14
Max 2.24 2.08 4.44 1.63 1.89 519.3 0.37 0.03
Mean 1.32 1.17 2.4 2.07 2.32 401.67 2.07 0.08
St.Dev 0.56 0.56 1.24 0.33 0.33 106.64 2.2 0.05
Groundwaters (n 21) SKK 1.38 1.22 2.47 2.83 3.09 239.16 1.41 0.02
OKK 0.35 0.19 1.27 2.87 3.12 272.36 0.72 0.01
S 0.45 0.30 0.59 2.28 2.53 316.37 2.20 0.05
AK 1.12 0.96 1.99 2.00 2.25 377.41 0.99 0.06
0.93 0.78 1.81 2.53 2.78 317.46 1.50 0.04
BST-1 0.79 0.64 1.43 2.46 2.72 363.13 0.25 0.01
BST-2 0.60 0.44 1.31 2.47 2.72 433.97 1.30 0.02
AT-1 1.10 0.95 2.35 1.49 1.74 729.76 1.65 0.26
IYKT-1 2.12 1.96 4.20 1.33 1.58 719.96 1.45 0.23
ZKT-1 1.15 1.00 1.16 1.64 1.90 393.27 1.31 0.06
KOY-1 0.62 0.47 1.03 2.11 2.36 416.6 0.23 0.01
BK-A 1.15 0.99 2.20 2.47 2.73 361.75 0.15 0.01
IG-1 0.89 0.74 1.81 1.32 1.57 602.17 0.17 0.03
IG-2 1.39 1.24 2.85 1.94 2.19 416.05 0.93 0.06
IG-3 1.99 1.84 4.39 0.92 1.17 1363.09 0.02 0.00
KOYM 0.20 0.05 0.91 2.42 2.67 521.51 0.06 0.01
K-1 0.75 0.60 1.12 1.93 2.18 310.93 0.44 0.05
K-2 0.80 0.65 1.51 1.85 2.1 358.25 0.79 0.07

PO-1 1.06 0.91 2.09 2.77 3.02 247.63 3.26 0.1
SKK 1.46 1.31 2.14 2.4 2.65 400.12 0.53 0.01
OK Kuyu 1.11 0.96 2.01 3.21 3.46 251.84 0.67 0.01
Min 0.2 0.05 0.59 3.21 3.46 239.16 3.26 0.26
Max 2.12 1.96 4.39 0.92 1.17 1363.09 0.15 0.01
Mean 1.02 0.87 1.94 2.15 2.41 448.23 0.94 0.05
St.Dev 0.48 0.48 0.97 0.59 0.59 251.13 0.82 0.07

Table 6
Measured values of environmental isotopes of the study area.

Sample No d2H () d18O () 3

H (TU)

Surface waters P-3 65.98 9.57 e

PP 67.54 9.80 e
F-1 63.53 9.37 e
F-3 61.50 8.25 e
Min 67.54 9.80
Max 61.50 8.25
Mean 64.64 9.25
St.Dev 2.66 0.69
Groundwaters SKK e e 7.39
OKK 68.68 10.45 6.26
S 72.23 10.36 e
AK 65.65 9.40 4.22
67.78 9.56 2.52
BST-2 68.72 9.89 8.38
AT-1 68.14 9.51 3.38
IYKT-1 70.00 9.99 3.11
ZKT-1 69.13 10.35 3.76
BK-A 65.71 10.16 6.47
IG-2 65.06 9.09 3.08
KOYM 64.75 9.74 e
K-1 65.42 9.05 1.66

PO-1 61.27 8.43 1.00
SKK 68.54 9.61 4.44
OK Kuyu 68.67 10.19 5.52
Min 72.23 10.45 1.00
Max 61.27 8.43 8.38
Mean 67.32 9.72 4.37
St.Dev 2.67 0.57 2.17
238 B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240

Fig. 9. Plot of d2H versus d18O of study area.

Fig. 10. Graph of d18O() versus Cl of groundwater in Ktahya Plain.

B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240 239

acidic and thus retards the soil natural fertility and lead to poor
plant growth and poor soil physical conditions.
In some of the water samples, the amount of Mg2, K, NO 3,
NO 2-
2 , SO4 and NH4 concentrations in groundwaters are above the
permissible limits of TSE-266 and WHO standards for drinking
water. Therefore, the government or any responsible body in the
area should take measures to control the anthropogenic activities
that cause the increase in these parameters.
To sum up, the current study suggestes that both natural and
anthropogenic processes contributed to being at high levels of
some chemical parameters of the groundwater in the Ktahya
Surface waters show more positive d2H and d18O than ground-
waters revealing evaporation effect on surface waters. Shallow
groundwaters had 3H from 2.52 to 8.38 TU. However, the two deep
groundwaters had 1 and 1.66 TU.
The municipal administrations in the study area should arrange
training, education programs and develop protection policies for
the agriculturalists about the type and the amount of fertilizers
used in order to increase local awareness of agricultural impacts on
groundwater and drinking water quality.


This work is supported by Ankara University BAP project (No.

Fig. 11. EC versus 3H (a) and d18O versus 3H(b) graph of the study area. 13L4343002). The authors are grateful for the constructive com-
ments and suggestions of the two anonymous reviewers for
improving the manuscript.
value d18O can suggest the circulation time. In Fig. 11b, decreasing
tritium content (TU) is observed from left to right, disclosing that
the general groundwater ow direction of the area.
Anandakumar, S., Subramani, T., Elango, L., 2009. Major ion groundwater chemistry
14. Conclusion of lower bahvani river basin, Tamil Nadu, India. J. Appl. Geochem. 11 (1),
APHA, 1989. Standard Methods for the Examination of Water and Wastewater,
The predominant cations and anions of surface and ground- seventeenth ed. American Public Health Association, Washington D.C.
water are Ca2 and Mg2, and HCO 3 respectively. Ca-Mg-HCO3 Ark, F., Yaldz, T., 2010. Heavy metal determination and pollution of the soil and
followed by Mg-Ca-HCO3 was the most dominant hydrochemical plants of Southeast Tavsanli (Kutahya, Turkey). Clean-Soil Air Water 38 (11),
facies in the study area. In the study area, water chemistry is pri- Berhe, B.A., elik, M., Dokuz, U.E., 2014. Determination of aquifer properties of the
marily controlled by water-rock interactions. Natural dissolution of Ktahya plain from a pumping and recovery test data. In: 67th Geological
carbonate rock (reaction between water and the limestone rocks of Congress of Turkey, Ankara, pp. 324e325.
Emet Formation) was the primary source of Ca2 and HCO 3 in
Clark, I., Fritz, P., 1997. Environmental Isotopes in Hydrogeology. Lewis Publishers,
Florida, pp. 112e136.
groundwater. The Mg2 ion is resulted from the water-rock inter- Cook, P.G., Herczeg, A.L., 1998. Groundwater Chemical Methods for Recharge
action in ophiolitic rocks of the study area. Perfect correlation be- Studies. CSIRO Publishing, Collingwood, Australia, pp. 1e5.
Craig, H., 1961. Isotopic variation in meteoric water. Science 133 (No. 3465),
tween EC and major ions indicates that EC is a measure of major ion
concentration in water samples. Craig, M., Johnson, T.M., 2008. Groundwater age and groundwater age dating. Annu.
Excess Na in Na versus Cl graph could result from silicate Rev. Earth Planet Sci. 36 (1), 121.
weathering reaction process or an anthropogenic activity. The ratio elik, M., nsal, N., Tfenki, O.O., Bolat, S., 2008. Assessment of water quality of the
lake seyfe basin, Krsehir, Turkey. Environ. Geol. 55, 559e569.
of Ca2/Mg2 of the surface and groundwater samples disclosing DSI, 1981. Ktahya Ve Ko proren Ovalar Hidrojeolojik Ett Raporu, 65 s. Devlet Su
the dissolution of calcite was dominant. About 81.5% waters of the _
Isleri Genel Mdrlg , Ankara, pp. 22e31.
DSI, 2003. Ktahya Ovas karst Hidrojeolojisi Ara Raporu, 41 s. Devlet Su Isleri, _
study area fall under very hard water category.
Eskisehir, pp. 7e13.
Chloro Alkaline Indices of the water reects the dominance of Elango, L., Kannan, R., Senthil, K.M., 2003. Major ion chemistry and identication of
direct ion-exchange of Na/K in the water with Ca2/Mg2 in the hydrogeochemical processes of groundwater in a part of Kancheepuram dis-
host rock. Therefore, it can be concluded that the geochemical trict, Tamil Nadu, India. J. Environ. Geoscience 10, 157e166.
Freeze, R.A., Cherry, J.A., 1979. Groundwater. Prentice Hall, Englewood Cliffs, New
process in the area that inuenced the chemical composition of the Jersey.
water sources is the dissolution of carbonate minerals, which Jalali, M., 2010. Groundwater geochemistry in the alisadr, hamadan, western Iran.
contributes the Ca2, Mg2, and HCO 3 to the groundwater. Environ. Monit. Assess. 166, 359e369.
Katz, B.G., Coplen, T.B., Bullen, T.D., Davis, J.H., 1998. Use of chemical and isotopic
In addition to the natural water-rock interaction, human activ- tracers to characterize the interaction between groundwater and surface water
ities are also the main causes to increase the concentrations of in mantled Karst. Groundwater 35 (6), 1014e1028.
some elements in groundwater. The positive correlation between Kavaf, N., Nalbantcilar, M.T., 2007. Assessment of contamination characteristics in
K- NO  2 2-
3 , K - NO2 , Mg -SO4 ions could be resulted from the usage
waters of the Kutahya plain, Turkey. Clean-Soil Air Water 35 (6), 585e1593.
Kendall, C., McDonnell, J.J., 1998. Isotope Tracers in Watershed Hydrology. Elsevier,
of excess amount of ammonium sulphate, ammonium nitrate, pp. 319e346.
magnesium sulphate, potassium nitrate and potassium sulphate KSM, 2012. Ktahya Il evre Durum Raporu Ktahya evre Ve Sehircilik Il
Mdrlg , Ktahya, pp. 101e103.
during agricultural practices.
LaBolle, E.M., Fogg, G.E., Eweis, J.B., 2006. Diffusive fractionation of 3H and 3He in
The presence of excess amount of ammonia, nitrate, nitrite and groundwater and its impact on groundwater age estimates. WRR 42 (W07202),
magnesium result from fertilizers in the soil making it, even more, 1e11.
240 B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240

Lucas, L.L., Unterweger, M.P., 2000. Comprehensive review and critical evaluation of Kullanarak Yerel Meteorik Dog _
rularn Belirlenmesi. 2. Ulusal Hidrolojide Izotop
the half-life of tritium. J. Res. Natl. Inst. Stand. Technol. 104 (4), 541e549. Tekniklerinin Kullanlmas Sempozyumu, Izmir,_ pp. 323e344.
Martinez, D.E., Bocanegra, E.M., 2002. Hydrogeochemistry and cation exchange Schoeller, H., 1967. Geochemistry of Groundwater. An International Guide for
processes in the coastal aquifers of Mar Del Plata, Argentina. Hydrogeol. J. 12, Research and Practice, vol. 15. UNESCO, pp. 1e18.
81e87. Seleem, E.G., 2014. Hydrochemistry of shallow groundwater around Quesna in-
Maya, A.L., Loucks, M.D., 1995. Solute and isotopic geochemistry and groundwater dustrial city, Egypt. J. Am. Sci. 10 (9), 90e97.
ow in the Central Wasatch Range, Utah. J. Hydrol. 172, 31e59. Sharma, P., Sharma, H.P., 2011. Groundwater quality assessment of Pachim Nalbari
Mazor, E., 2004. Chemical and Isotopic Groundwater Hydrology. Marcel Dekker, Inc, block of Nabari district Assam based on major ion chemistry. Int. J. chemTech
New York. Res. 3 (4), 1914e1917.
Meybeck, M., 1987. Global chemical weathering of surcial rocks estimated from Todd, D.K., 1980. Groundwater Hydrology, 2rd ed. John Wiley and Sons, New York.
river dissolved loads. Am. J. Sci. 287, 401e428. _
TSE-266, 2005. Ime Sular Standard. Trk Standartlar Enstits, vol. 266. Bask
Nagaraju, A., Suresh, S., Killham, K., Hudson, E.K., 2006. Hydrogeochemistry of TSE, TS, Ankara, pp. 1e25.
waters of mangampeta barite mining area, cuddapah basin, Andhra Pradesh, UNEP/WHO, 1996. Water Quality Monitoring - a Practical Guide to the Design and
India. Turk. J. Eng. Env.Sci. 30, 203e219. Implementation of Freshwater Quality Studies and Monitoring Programmes.

Ozburan, M., 2009. Neotectonic Investigation of Ktahya and its Surrounding. Published on behalf of United Nations Environment Programme and the World
Dissertation. Kocaeli University. Health Organization.
Piper, A.M., 1944. A graphical procedure in the geochemical interpretation of water Weissmann, G.S., Zhang, Y., LaBolle, E.M., Fogg, G.E., 2002. Dispersion of Ground-
analysis. Trans. Am. Geophys. Union 25, 914e928. water Age in an Alluvial Aquifer System, vol. 38. WRR, California, USA,
Richter, B.C., Kreitler, C.W., 1993. Geochemical Techniques for Identifying Sources of pp. 1198e1211.
Groundwater Salinization. CRC Press, Inc, Boca Raton, Florida, pp. 188e201. WHO, 2008. Guidelines to Drinking Water Quality. World Health Organisation,
Sayn, M., Eypog 2005. Trkiyedeki Yag
lu, S.O., slarn Kararl Izotop Ieriklerini Geneva, pp. 289e405.