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Assessment of hydrogeochemistry and environmental isotopes of surface and groundwaters in the Kütahya Plain, Turkey
Journal of African Earth Sciences 134 (2017) 230e240
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Journal of African Earth Sciences journal homepage: www.elsevier.com/locate/jafrearsci
Assessment of hydrogeochemistry and environmental isotopes of surface and groundwaters in the Kütahya Plain, Turkey ur Erdem Dokuz b, Mehmet Çelik c Berihu Abadi Berhe a, *, 1, Ug an, Ankara, Turkey Ankara University, Graduate School of Applied Science, Geological Engineering Dept., 06100, Tandog € de, Turkey Omer Halisdemir University, Faculty of Engineering, Geological Engineering Dept., 51240, Nig c €lbas¸ı, Ankara, Turkey Ankara University, Faculty of Engineering, Geological Engineering Dept., 50th Year Campus, 06830, Go a
b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 31 January 2017 Received in revised form 20 May 2017 Accepted 22 June 2017 Available online 22 June 2017
The aim of the present work is to determine the geochemical processes that control the nature of the groundwater and assess the quality of water for drinking and public health purposes. Surface and groundwater samples of Kütahya plain were analyzed for their physio-chemical and environmental isotope properties. The relative concentrations of the water ions were found to occur in the order of 2Ca2þ>Mg2þ>(Kþ þ Naþ) and HCO 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 d2H and 9.25 d18O. Tritium activities in groundwater from the wells ranged from 1.00 to 8.38 TU with a mean value of 4.37 TU. The impact of agricultural practices and poor sanitation conditions is indicated by þ þ 2þ the positive correlation between Kþ - NO ions 3 , K - NO2 and HCO3 - Cl ions as well as Na and Mg with SO2 4 ion. The groundwater quality of Kütahya plain is influenced by various natural and anthropogenic factors. © 2017 Elsevier Ltd. All rights reserved.
Keywords: Hydrogeochemistry Water quality Water types Isotopes Geochemical evolution Kütahya plain
1. Introduction Groundwater is one of the most crucial resources for human life. The quality of water depends upon the geological environment, natural movement and human activities. Nowadays, basic demands for fresh water are for the purpose of irrigation, household and municipal water use, and industrial uses (UNEP/WHO, 1996). The present study area, Kütahya plain and its catchment lies between 225000 and 268000E longitude and 4345000e4380000N latitude with an area of around 93 km2 and its total catchment covers about 550 km2. It is crossed by two perennial rivers called the Felent and the Porsuk Rivers (Fig. 1). According to the data recorded at Kütahya Meteorological Station between the years 1975 and 2011, the mean annual precipitation and air temperature are 543.85 mm and 10.81 C, respectively. € prüo €ren plain and The study area is located in downstream of Ko
* Corresponding author. E-mail address: [email protected] (B. Abadi Berhe). 1 Wollo University, College of Natural Science, Department of Geology, 1145, Dessie, Ethiopia. http://dx.doi.org/10.1016/j.jafrearsci.2017.06.015 1464-343X/© 2017 Elsevier Ltd. All rights reserved.
upstream of Porsuk dam the water of which is used by people living in Eskis¸ehir and Kütahya for both irrigation and domestic purposes. Heavy metal concentrations in soil samples and leaves of trees and € prüo € ren basin have relatively higher conherbaceous plants in Ko centrations (Arık and Yaldız, 2010).The waters form spring, rivers and groundwaters of Kütahya plain contain As, Pb, and U concentrations and the As concentration in all waters is above the maximum contaminant level (Kavaf and Nalbantcilar, 2007). In the study area, people of this district and surrounding villages are the primary users of groundwater for drinking, industrial and irrigation and the surface water irrigation for purposes. The area is one of the Turkey's regions experiencing an exponential growth of intensive agriculture and industrial activity. The interactions between agricultural irrigation, surface water and groundwater resources are always very close. The agricultural activities and industrial establishments in Kütahya city such as sugar factories, nitrogen and magnesium factories and leather industries are responsible for disposing of treated and untreated effluents in the natural drainage system of the Felent and the Porsuk rivers. The most common nitrogen fertilizer currently used in all the agricultural lands of the Kütahya plain are urea (CO(NH2)2), DAP
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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
((NH4)2HPO4), ammonium sulphate ((NH4)2SO4), ammonium nitrate (NH4NO3), magnesium sulphate (MgSO4), potassium nitrate (KNO3) and potassium sulphate (K2SO4) (KÇS¸M, 2012). Hydrogeochemical processes such as dissolution, precipitation, ion exchange and the residence time along the flow path govern chemical compositions of groundwater (Martinez and Bocanegra, 2002). The main objective of the present work is to investigate the geochemical processes that control the nature of the groundwater and assess the quality of water for drinking and public health purposes. The study was performed using hydrochemical and environmental isotopic data of oxygen-18, deuterium and tritium.
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 field using standard field equipment (Multi 350i multiparameter). Water samples were filtered using 0.45-mm disposable capsule filter 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 fitting covers. The analysis was done using DIONEX LC25, ICS-1000 High-Performance Ion Chromatography system, YSI MPS 556 Multi-probe system, and 2Automatic acid titration burette (for HCO 3 and CO3 ) at Hacettepe University Water Chemistry Laboratory in Ankara, Turkey. The American Public Health Association (APHA, 1989) standard Methods were used for the Examination of Water and Wastewater. The stable isotopic analyses were performed at the Laboratory of the international research and application center for karst water resources in Hacettepe University, Ankara, Turkey (Berhe et al., 2014). The hydrochemical results were plotted on Piper diagram using AquaChem 5.1 software. Statistical descriptive analysis and correlation between different parameters of waters were done by SPSS software package version 16.0. Mineral saturation index of all water 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 ürler Complexes, SabSarıcasu Formation, Arıkaya Formation, Çüg €ren Formation uncupınarı Formation, Emet Formation, Parmako and Alluvials (Fig. 2). The basement rocks are comprised of meta€g ürler Complexes rocks (DSI, 1981; morphic schists, Marbles and Ço € DSI, 2003; Ozburan, 2009). Sarıcasu Formation of Paleozoic age is composed of schists, calcschist, quartz schist and crystallized limestone and overlain by Arıkaya Formation of Upper Permian-Lower Triassic age, Marble. Crystalline limestones unconformably overlie the Çayca Tuf and at the top, and it is unconformably covered by Pleistocene age of €ren Formation and alluvials. The Quaternary alluvial, Parmako which covers the plain, comprises fluviatile pebble, gravel, sand, and silt, is widely distributed in this plain, and has a maximum depth of 100 m. The gravely and sandy horizons in Kütahya plain form one of the best aquifers. The mean hydraulic conductivity (K) and transmissivity (T) obtained from analysis of pumping test and recovery data for this aquifer were 44.42 m/day and 213.48 m2/day, € ren Forrespectively. The sandstone and gravelstone of Parmako mation are permeable material and its mean value of hydraulic
The physicochemical parameters of surface water samples collected from the Felent and Porsuk Rivers and groundwaters in December 2013 were compiled in Table 1. The average water temperature, pH and electrical conductivity values of the surface waters were 13.2 C, 8.43 and 907.25 mS/cm whereas groundwater samples had 13.21 C, 8.18 and 1006.90 mS/cm, respectively. The pH values of all waters used in the study area elaborate a trend of alkaline chemical reaction within the groundwater system (Tables 1 and 2). Minimum, maximum and mean concentrations of ions present in surface and groundwater from the study area are presented in Tables 1 and 2. The relative concentrations of the surface and groundwater ions occur in the order of Ca2þ>Mg2þ>(Kþ þ Naþ) and 2 HCO 3 >SO4 >Cl . The predominant cations of surface waters were Ca2þ and Mg2þ with a mean value of ion concentration 96.42 and 38.68 mg/l, respectively, whereas HCO 3 with a mean value of 441.21 mg/l was a dominant anion. Among the major cations of groundwater of the plain same as surface waters Ca2þ and Mg2þ were again predominates and their average concentration were 92.57 and 52.82 mg/l respectively. Among the major anions, HCO 3 with an average concentration of 414.45 mg/l was the dominant ion
Fig. 1. Location of study area and sampling points.
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€ Fig. 2. Geological map of the study area (modified from DSI, 1981; 2003; Ozburan, 2009).
(Tables 1 and 2, and Fig. 4). 5. Hydrochemical facies Piper diagram is the most convenient way for plotting the results of multiple analyses on the same graph, which may disclose grouping of certain samples and show different hydrochemical facies or origin of groundwater (Piper, 1944). By using the Piper diagram, the surface and groundwaters of the study area can be categorized into the following groups: Ca-Mg-HCO3 (66.67%), MgCa-HCO3 (18.52%), Ca-HCO3 (7.41%), Mg-Ca-SO4-HCO3 (3.7%) and Mg-Ca-HCO3-SO4 (3.7%), revealing that the Ca-Mg-HCO3 water type 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 are from the same origin. 6. Drinking water quality The analytical physio-chemical parameters of groundwater were compared with the standard guideline values as recommended by the Turkish Standards Institution (TSE-266, 2005) and World Health Organization (WHO, 2008) for drinking and public health purposes (Table 2). Temperature, pH (except 3 samples according to WHO), and the concentration of ions, such as Naþ, Ca2þ, PO34 , F and Cl in the investigated groundwater samples were within the maximum permissible limits TSE-266 and WHO standards. Only one of the groundwater samples exceeded the EC limit of TSE-266 standard, but two samples according to WHO. Furthermore, 23.8% of the samples exceeded the hardness permissible limit of WHO. The concentration of Mg2þ shows that 28.3% and 4.7% of the samples exceeded the acceptable limits of TSE-266 and WHO, respectively. Although Kþ concentration of the groundwater is very low as
compared to Ca2þ and Mg2þ ions, 3 water samples were found out above allowable TSE-266 limits. Nevertheless, none of them were above WHO limits (Table 2). The nitrate concentration value obtained from two water samples was higher than that of TSE-266 and WHO limits for drinking water. The results of nitrite concentration of study area depict that 4 water samples exceeded the allowable limits of TSE-266. However, comparing with permissible limits of WHO all water samples are under the limits. NHþ 4 concentration of water samples disclosed that about 33.3% and 4.7% were above the permissible limits of TSE266 and WHO, respectively (Table 2). The concentration of SO24 in groundwater reveals that only one water sample exceeded the standard allowable limits of TSE-266 and WHO for SO24 (Table 2). 7. Composition diagrams The most acceptable method to classify and compare intermixing fresh and saline waters based on ionic composition is by plotting the chemical data on a composition diagrams. Mixing lines indicate the mix of contaminated and fresh end members in various proportions (Mazor, 2004). The surface and groundwaters vary notably in their chemical concentrations, the data plot on straight lines is an indication for a positive correlation between Ca2þ, Mg2þ, 2 Naþ, HCO 3 , SO4 and Cl with the total dissolved ion (TDI) (Fig. 5). Fig. 5a and d shows that the line extrapolating to values on the Ca2þ and HCO 3 axis indicates that both intermixing waters contain a significant concentration of Ca2þ and HCO 3 . In Fig. 5b, c, e and f, the line extrapolates to point in the TDI line, showing the fresh end member contains a significant concentration of ions other than Mg2þ, Naþ, SO24 and Cl . 8. Correlation coefficient analysis The correlation coefficient is a vital method in building the
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Fig. 3. Hydrogeological cross sections. Lines of section indicated on Fig. 2.
relationship between two variables (Anandakumar et al., 2009). Pairs that have high positive correlation show the dependency of one parameter on the other (Sharma and Sharma, 2011). Correlations between major ions in surface and groundwater within the study area were carried out using Pearson's correlation analysis in SPSS 16.0 program (Table 3). Correlation coefficients of major and some minor ions were computed using values of concentrations of the different ions in mg/l. The high correlation co 2þ efficient between Naþ- Cl, Mg2þ - HCO 3 and Ca - HCO3 ions was observed. Therefore, it can be concluded that for most of the water 2þ samples of the area Naþ and Cl, Mg2þ and HCO and HCO 3 , Ca 3 have originated from the common source. Perfect correlation be2 tween EC and major ions (Ca2þ, Mg2þ, Naþ, HCO 3 , Cl and SO4 ) indicates that EC is a measure of major ion concentration in water samples. There is a very high positive correlation between Kþ- NO 3 2 2 2 (r ¼ 0.97), Kþ- NO 2 (r ¼ 0.84) and HCO3 Cl (r ¼ 0.83) ions as
well as Naþ and Mgþ2 ions with SO24 ion, indicating the anthropogenic impact from agricultural practices and poor sanitation conditions. Other moderately inter-relationships exist as shown in Table 3. 9. Molar ratio between major ions Naþ/Cl¡ relations: When halite dissolution is accountable for sodium, the Naþ/Cl molar ratio is nearly one, whereas a ratio >1, it is typically deduced that Naþ is released from a silicate weathering reaction (Meybeck, 1987). In the current study area, Naþ/Cl molar ratio generally ranges from 0.69 to 6.36 with an average of 1.78. In a plot of Naþ against Cl (Fig. 6), most of the samples lie above 1:1 trend line showing excess Naþ. This excess Naþ may be the result of silicate weathering reaction process or anthropogenic activities. Ca2þ/Mg2þ relations: In the study area, the dominant cations were calcium and magnesium, while bicarbonate was dominant
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Table 1 Statistical descriptive of physicochemical of surface waters (n ¼ 6) of the study area. Parameters
Units
Min
Max
Mean
St.dev
Ph T EC Liþ NHþ 4 Kþ þ Na Mg2þ Ca2þ PO34 Br F NO 2 NO 3 Cl SO24 HCO 3 TDI
e C mS/cm mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l meq/l
7.70 10.30 613 0.00 0.00 2.61 9.74 21.32 81.02 0.00 0.02 0.08 0.17 0.19 2.36 9.05 337.57 12.26
9.67 15.20 1111 0.02 13.14 30.51 31.97 63.95 119.66 0.69 0.17 0.31 1.31 19.9 31.4 90.03 574.47 22.22
8.43 13.20 907.25 0.01 2.77 9.19 22.05 38.68 96.42 0.23 0.07 0.21 0.50 6.01 19.65 42.73 441.21 18.15
0.74 1.89 231.92 0.01 5.23 10.59 9.78 19.05 15.59 0.27 0.05 0.08 0.43 7.51 12.1 33.42 86.94 4.64
et al., 1998; Elango et al., 2003). In the study area, the Ca2þ/Mg2þ ratio of the surface and groundwater samples ranged between 0.25 and 12.86 and its mean value was 1.88 (Fig. 7). About 77.8% samples had a ratio <2 disclosing the dissolution of calcite, whereas the rest 22.2% samples had a ratio >2, which indicates the effect of silicate minerals. 2þ (Ca2þ þ Mg2þ)/HCO¡ 3 relations: Appraisal of the slopes of Ca 2þ and Mg versus HCO3 gives crucial information about the sources of Ca2þ and Mg2þ in groundwater (Richter and Kreitler, 1993). Dissolution of silicate and oxidation of organic matter may have produced the excess HCO3- in the groundwater (Seleem, 2014). In the study area, a plot of Ca2þ þ Mg2þ versus HCO3 shows that about 96.2% of sampled waters plot below the 1:1 aquiline (Fig. 8). This indicates a deficiency of Ca2þ þ Mg2þ relative to HCO3-. Therefore, some HCO 3 is also coming from processes other than calcite or dolomite dissolution, or the Ca2þ and Mg2þ are lost in the cation exchange reactions and it might have been balanced by Naþ and Kþ or supplied by silicate weathering.
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
Ph T EC Hardness Liþ NHþ 4 Kþ Naþ Mg2þ Ca2þ PO34 Br F NO 2 NO 3 Cl 2SO4 HCO 3 TDI
e C mS/cm mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l meq/l
Groundwater (n ¼ 21)
TSE (266) 2005
WHO (2008)
Min
Max
Mean
St.dev
Maximum permissible No. of samples > standard limit Maximum permissible No. of samples > standard limit
7.49 8.50 483.00 239.16 0.00 0.00 0.60 2.27 6.89 21.93 0.00 0.00 0.00 0.11 0.07 1.78 2.73 275.39 9.67
9.11 17.1 3135 1363.09 0.09 3.10 158.99 105.54 237.91 154.3 1.39 0.47 0.43 2.94 225.43 173.94 649.43 731.41 62.70
8.18 13.21 1006.9 448.23 0.02 0.61 17.18 22.59 52.82 92.57 0.23 0.09 0.21 0.48 28.35 29.62 76.91 414.45 20.14
0.43 1.78 647.11 251.13 0.02 0.72 42.69 27.12 48.56 35.45 0.37 0.11 0.13 0.63 57.45 42.79 142.7 119.22 12.94
6.5e9.2 25 2000 e e 0.05e0.5 12 175 50 200 5 e 1.5 0.1 50 600 250 e
None None 2 e e 7 3 None 5 None None e None 16 2 None 1 e
6.5e8.5 30 1500 500 e 1.5 50 200 150 250 6.5 e 1.5 3 50 250 250 e
3 None 2 5 e 1 None None 1 None None e None None 2 None 1 e
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 ¼ 2:5 Ca2þ þ 4:1 Mg2þ
Fig. 4. Piper diagrams of surface and groundwaters in Kütahya Plain.
anion in groundwater. The points plotted on the line Ca2þ/Mg2þ ¼ 1 indicate waters controlled by dolomite dissolution while the Ca2þ/ Mg2þ ratio ranging from 1 to 2 characterizes the dissolution of calcite (Maya and Loucks, 1995). In natural waters, Ca2þ/Mg2þ ratio greater than 2 is mainly due to the dissolution of silicate minerals, which contribute calcium and magnesium in groundwater (Katz
(1)
Where TH, Ca2þ and Mg2þconcentrations are all in mg/l (Todd, 1980). 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) classification, 18.5% of the water samples are hard, while 81.5% falls under very hard category (Tables 4 and 5). 11. Ion exchange Chloro Alkaline Indices (CAI): Schoeller (1967) has formulated a formula used to be known as the ion exchange between the
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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 ¼ 0), undersaturated (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 undersaturated with respect to sulphate minerals (anhydrite and gypsum) (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
Fig. 5. A composition diagram of surface and groundwater of Kütahya Plain. Concentrations are given in meq/l.
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 represented by the equation: d2H ¼ 8d18O þ 10 (Craig, 1961). Moreover, the Local Meteoric Line established for Isparta (ILMWL) is
Table 3 Correlation coefficients between major ions in surface and groundwaters of study area. Parameter
pH
EC
Liþ
NHþ 4
Kþ
Naþ
Mg2þ
Ca2þ
PO34
Br
F
NO 2
NO 3
Cl
SO24
HCO 3
pH EC Liþ NHþ 4 Kþ þ Na Mg2þ Ca2þ PO34 Br F NO 2 NO 3 Cl 2SO4 HCO 3
1 0.28 0.08 0.23 0.11 0.27 0.31 0.15 0.07 0.29 0.27 0.07 0.12 0.29 0.33 0.16
1 0.45 0.10 0.55 0.96 0.92 0.71 0.26 0.93 0.53 0.50 0.49 0.99 0.92 0.90
1 0.04 0.87 0.54 0.22 0.36 0.78 0.36 0.45 0.68 0.84 0.44 0.22 0.39
1 0.08 0.22 0.06 0.02 0.12 0.13 0.14 0.18 0.16 0.13 0.12 0.19
1 0.59 0.32 0.41 0.62 0.41 0.32 0.84 0.97 0.52 0.24 0.55
1 0.85 0.66 0.30 0.93 0.64 0.47 0.51 0.97 0.89 0.83
1 0.43 0.07 0.88 0.49 0.33 0.27 0.92 0.95 0.76
1 0.25 0.62 0.27 0.37 0.36 0.65 0.57 0.79
1 0.16 0.36 0.49 0.59 0.21 0.05 0.31
1 0.62 0.26 0.31 0.95 0.92 0.79
1 0.21 0.26 0.56 0.52 0.42
1 0.84 0.45 0.21 0.54
1 0.47 0.19 0.45
1 0.94 0.83
1 0.72
1
Strong correlations between two parameters are showed in bold numbers.
groundwater and its surroundings during residence or travelling in the aquifer (eq (2) and (3)). Positive CAI indicates the exchange of Naþ and K from the water with Mg2þ and Ca2þ of the rocks and is negative when there is an exchange of Mg2þ and Ca2þ of the water with Naþ and Kþ of the rocks (Nagaraju et al., 2006; Çelik et al., 2008).
CAI1 ¼
CAI2 ¼
Cl Naþ þ Kþ Cl
Cl Naþ þ Kþ
(2)
SO2 þ HCO 4 3 þ CO3 þ NO3
(3)
According to Table 5, 92.6% of the samples from the study area showed negative ratios indicating an indirect base-exchange reaction. During this process, the host rocks were not considered to be the principal sources of dissolved solids in the water and reflected the dominance of direct ion-exchange of Naþ/Kþ in the water with Mg2þ/Ca2þ in the host rock.
€ 2005). Variations in the d2H ¼ 8d18O þ 12.16 (Sayın and EyüpogluO, stable-isotope signature of groundwater are due to natural variations in the isotopic composition of rainfall such as mixing with pre-existing waters, and evaporation during percolation through the soil and/or the unsaturated zone (Kendall and McDonnell, 1998). 19 water samples for stable isotope analyses (oxygen and hydrogen isotopes) were collected during December 2013 from surface water, shallow and deep groundwater through December 2013 (Table 6) and were plotted as can be seen in Fig. 9. The measured d2H and d18O values of surface water samples collected during this study range from 67.54 to 61.50 and 9.80 to 8.25, respectively. On the other hand, groundwaters range from 72.23 to 61.27 and from 10.45 to 8.43, respectively. The result is disclosing that the surface and groundwaters are isotopically depleted (Table 6). The groundwaters have a mean isotopic composition of 67.32 (d2H) and 9.72 (d18O) and these values are comparatively lower than surface waters 64.64 (d2H) and 9.25 (d18O), thus surface waters are more positive than groundwaters
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Na+ (mmol)
5 4
ine
l 1:1
3 2 1 0 0
1
2
3
4
5
6
Cl- (mmol) Fig. 6. Naþ versus Clgraph.
Table 4 Hardness of waters.
Fig. 7. Ca2þ/Mg2þ ratio graph of water samples.
Hardness
Water classification
% Result of this study
0e75 75e150 150e300 >300
Soft Moderately hard Hard Very hard
e e 18.5 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 undergone some evaporation before or during their underground transportation system (Fig. 9). Clark and Fritz (1997) established d18O-Cl- relationship graph 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 ¼ 0.076) (Fig. 10). This implies that even if evaporation occurs, its impact upon the salinization of groundwater may be insignificant.
13.2. Tritium
Fig. 8. Ca2þ þ Mg2þ against HCO 3 graph.
revealing evaporation effect on surface waters. However, they are generally similar and are plotted on the same area on d2H - d18O, indicating that they have originated from the same source, which supports the Piper graph. The diagram d2H - d18O shows that the surface and groundwater plot on/or is close those of ILMWL and the GMWL suggesting their
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. 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 of 4.37 TU (Table 6). The tritium contents in shallow groundwater ranged from 2.52 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, indicating the presence of relatively old groundwater in this part (Fig. 11a). The graph of tritium content of groundwater and its measured
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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 Surface waters (n ¼ 6)
Groundwaters (n ¼ 21)
SIcalcite
SIaragonite
SIdolomite
SIgypsum
SIanhydrite
TH
CAI1
CAI2
PÇ-3 PÇP PÇÇ FÇ-1 FÇ-2 FÇ-3 Min Max Mean St.Dev SKK OKK SÇ AKÇ ÇÇ BST-1 BST-2 AT-1 _ IYKT-1
1.09 1.38 0.67 2.24 1.62 0.94 0.67 2.24 1.32 0.56 1.38 0.35 0.45 1.12 0.93 0.79 0.60 1.10 2.12
0.94 1.23 0.51 2.08 1.46 0.79 0.51 2.08 1.17 0.56 1.22 0.19 0.30 0.96 0.78 0.64 0.44 0.95 1.96
1.78 2.37 1.03 4.44 3.17 1.61 1.03 4.44 2.4 1.24 2.47 1.27 0.59 1.99 1.81 1.43 1.31 2.35 4.20
2.58 2.17 2.09 1.77 1.63 2.15 2.58 1.63 2.07 0.33 2.83 2.87 2.28 2.00 2.53 2.46 2.47 1.49 1.33
2.83 2.42 2.34 2.03 1.89 2.40 2.83 1.89 2.32 0.33 3.09 3.12 2.53 2.25 2.78 2.72 2.72 1.74 1.58
295.49 306.52 316.37 510.03 519.3 462.33 295.49 519.3 401.67 106.64 239.16 272.36 316.37 377.41 317.46 363.13 433.97 729.76 719.96
6.37 1.78 1.48 0.50 0.37 1.89 6.37 0.37 2.07 2.2 1.41 0.72 2.20 0.99 1.50 0.25 1.30 1.65 1.45
0.07 0.05 0.12 0.04 0.03 0.14 0.14 0.03 0.08 0.05 0.02 0.01 0.05 0.06 0.04 0.01 0.02 0.26 0.23
ZKT-1 KOY-1 BK-A _ IG-1
1.15 0.62 1.15 0.89
1.00 0.47 0.99 0.74
1.16 1.03 2.20 1.81
1.64 2.11 2.47 1.32
1.90 2.36 2.73 1.57
393.27 416.6 361.75 602.17
1.31 0.23 0.15 0.17
0.06 0.01 0.01 0.03
_ IG-2 _ IG-3 KOYM K-1 K-2 € PO-1
1.39
1.24
2.85
1.94
2.19
416.05
0.93
0.06
1.99
1.84
4.39
0.92
1.17
1363.09
0.02
0.00
0.20 0.75 0.80 1.06
0.05 0.60 0.65 0.91
0.91 1.12 1.51 2.09
2.42 1.93 1.85 2.77
2.67 2.18 2.1 3.02
521.51 310.93 358.25 247.63
0.06 0.44 0.79 3.26
0.01 0.05 0.07 0.1
SKÇK OK Kuyu Min Max Mean St.Dev
1.46 1.11 0.2 2.12 1.02 0.48
1.31 0.96 0.05 1.96 0.87 0.48
2.14 2.01 0.59 4.39 1.94 0.97
2.4 3.21 3.21 0.92 2.15 0.59
2.65 3.46 3.46 1.17 2.41 0.59
400.12 251.84 239.16 1363.09 448.23 251.13
0.53 0.67 3.26 0.15 0.94 0.82
0.01 0.01 0.26 0.01 0.05 0.07
Table 6 Measured values of environmental isotopes of the study area.
d2H (‰)
d18O (‰)
3
PÇ-3 PÇP FÇ-1 FÇ-3 Min Max Mean St.Dev SKK OKK SÇ AKÇ ÇÇ BST-2 AT-1 _ IYKT-1
65.98 67.54 63.53 61.50 67.54 61.50 64.64 2.66 e 68.68 72.23 65.65 67.78 68.72 68.14 70.00
9.57 9.80 9.37 8.25 9.80 8.25 9.25 0.69 e 10.45 10.36 9.40 9.56 9.89 9.51 9.99
e e e e
7.39 6.26 e 4.22 2.52 8.38 3.38 3.11
ZKT-1 BK-A _ IG-2
69.13 65.71 65.06
10.35 10.16 9.09
3.76 6.47 3.08
KOYM K-1 € PO-1
64.75 65.42 61.27
9.74 9.05 8.43
e 1.66 1.00
SKÇK OK Kuyu Min Max Mean St.Dev
68.54 68.67 72.23 61.27 67.32 2.67
9.61 10.19 10.45 8.43 9.72 0.57
4.44 5.52 1.00 8.38 4.37 2.17
Sample No Surface waters
Groundwaters
H (TU)
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Fig. 9. Plot of d2H versus d18O of study area.
Fig. 10. Graph of d18O(‰) versus Cl of groundwater in Kütahya 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 Mg2þ, Kþ, NO 3, 2þ NO 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 Kütahya plain. Surface waters show more positive d2H and d18O than groundwaters 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. Acknowledgment
Fig. 11. EC versus 3H (a) and d18O versus 3H(b) graph of the study area.
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 flow direction of the area. 14. Conclusion The predominant cations and anions of surface and groundwater are Ca2þ and Mg2þ, and HCO 3 respectively. Ca-Mg-HCO3 followed by Mg-Ca-HCO3 was the most dominant hydrochemical facies in the study area. In the study area, water chemistry is primarily controlled by water-rock interactions. Natural dissolution of carbonate rock (reaction between water and the limestone rocks of Emet Formation) was the primary source of Ca2þ and HCO 3 in groundwater. The Mg2þ ion is resulted from the water-rock interaction in ophiolitic rocks of the study area. Perfect correlation between EC and major ions indicates that EC is a measure of major ion concentration in water samples. Excess Naþ in Naþ versus Cl graph could result from silicate weathering reaction process or an anthropogenic activity. The ratio of Ca2þ/Mg2þ of the surface and groundwater samples disclosing the dissolution of calcite was dominant. About 81.5% waters of the study area fall under very hard water category. Chloro Alkaline Indices of the water reflects the dominance of direct ion-exchange of Naþ/Kþ in the water with Ca2þ/Mg2þ in the host rock. Therefore, it can be concluded that the geochemical process in the area that influenced the chemical composition of the water sources is the dissolution of carbonate minerals, which contributes the Ca2þ, Mg2þ, and HCO 3 to the groundwater. In addition to the natural water-rock interaction, human activities are also the main causes to increase the concentrations of some elements in groundwater. The positive correlation between þ 2þ 2Kþ- NO 3 , K - NO2 , Mg -SO4 ions could be resulted from the usage of excess amount of ammonium sulphate, ammonium nitrate, magnesium sulphate, potassium nitrate and potassium sulphate during agricultural practices. The presence of excess amount of ammonia, nitrate, nitrite and magnesium result from fertilizers in the soil making it, even more,
This work is supported by Ankara University BAP project (No. 13L4343002). The authors are grateful for the constructive comments and suggestions of the two anonymous reviewers for improving the manuscript. References Anandakumar, S., Subramani, T., Elango, L., 2009. Major ion groundwater chemistry of lower bahvani river basin, Tamil Nadu, India. J. Appl. Geochem. 11 (1), 92e101. APHA, 1989. Standard Methods for the Examination of Water and Wastewater, seventeenth ed. American Public Health Association, Washington D.C. Arık, F., Yaldız, T., 2010. Heavy metal determination and pollution of the soil and plants of Southeast Tavsanli (Kutahya, Turkey). Clean-Soil Air Water 38 (11), 1017e1030. Berhe, B.A., Çelik, M., Dokuz, U.E., 2014. Determination of aquifer properties of the Kütahya plain from a pumping and recovery test data. In: 67th Geological Congress of Turkey, Ankara, pp. 324e325. Clark, I., Fritz, P., 1997. Environmental Isotopes in Hydrogeology. Lewis Publishers, Florida, pp. 112e136. Cook, P.G., Herczeg, A.L., 1998. Groundwater Chemical Methods for Recharge Studies. CSIRO Publishing, Collingwood, Australia, pp. 1e5. Craig, H., 1961. Isotopic variation in meteoric water. Science 133 (No. 3465), 1702e1703. Craig, M., Johnson, T.M., 2008. Groundwater age and groundwater age dating. Annu. Rev. Earth Planet Sci. 36 (1), 121. Çelik, M., Ünsal, N., Tüfenkçi, O.O., Bolat, S., 2008. Assessment of water quality of the lake seyfe basin, Kırs¸ehir, Turkey. Environ. Geol. 55, 559e569. €prüo €ren Ovaları Hidrojeolojik Etüt Raporu, 65 s. Devlet Su DSI, 1981. Kütahya Ve Ko _ ¸ leri Genel Müdürlüg ü, Ankara, pp. 22e31. Is _ ¸ leri, DSI, 2003. Kütahya Ovası karst Hidrojeolojisi Ara Raporu, 41 s. Devlet Su Is Eskis¸ehir, pp. 7e13. Elango, L., Kannan, R., Senthil, K.M., 2003. Major ion chemistry and identification of hydrogeochemical processes of groundwater in a part of Kancheepuram district, Tamil Nadu, India. J. Environ. Geoscience 10, 157e166. Freeze, R.A., Cherry, J.A., 1979. Groundwater. Prentice Hall, Englewood Cliffs, New Jersey. Jalali, M., 2010. Groundwater geochemistry in the alisadr, hamadan, western Iran. Environ. Monit. Assess. 166, 359e369. Katz, B.G., Coplen, T.B., Bullen, T.D., Davis, J.H., 1998. Use of chemical and isotopic tracers to characterize the interaction between groundwater and surface water in mantled Karst. Groundwater 35 (6), 1014e1028. Kavaf, N., Nalbantcilar, M.T., 2007. Assessment of contamination characteristics in 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, pp. 319e346. KÇS¸M, 2012. Kütahya Il Çevre Durum Raporu Kütahya Çevre Ve S¸ehircilik Il ü, Kütahya, pp. 101e103. Müdürlüg LaBolle, E.M., Fogg, G.E., Eweis, J.B., 2006. Diffusive fractionation of 3H and 3He in groundwater and its impact on groundwater age estimates. WRR 42 (W07202), 1e11.
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Lucas, L.L., Unterweger, M.P., 2000. Comprehensive review and critical evaluation of the half-life of tritium. J. Res. Natl. Inst. Stand. Technol. 104 (4), 541e549. Martinez, D.E., Bocanegra, E.M., 2002. Hydrogeochemistry and cation exchange processes in the coastal aquifers of Mar Del Plata, Argentina. Hydrogeol. J. 12, 81e87. Maya, A.L., Loucks, M.D., 1995. Solute and isotopic geochemistry and groundwater flow in the Central Wasatch Range, Utah. J. Hydrol. 172, 31e59. Mazor, E., 2004. Chemical and Isotopic Groundwater Hydrology. Marcel Dekker, Inc, New York. Meybeck, M., 1987. Global chemical weathering of surficial rocks estimated from river dissolved loads. Am. J. Sci. 287, 401e428. Nagaraju, A., Suresh, S., Killham, K., Hudson, E.K., 2006. Hydrogeochemistry of waters of mangampeta barite mining area, cuddapah basin, Andhra Pradesh, India. Turk. J. Eng. Env.Sci. 30, 203e219. € Ozburan, M., 2009. Neotectonic Investigation of Kütahya and its Surrounding. Dissertation. Kocaeli University. Piper, A.M., 1944. A graphical procedure in the geochemical interpretation of water analysis. Trans. Am. Geophys. Union 25, 914e928. Richter, B.C., Kreitler, C.W., 1993. Geochemical Techniques for Identifying Sources of Groundwater Salinization. CRC Press, Inc, Boca Raton, Florida, pp. 188e201. € 2005. Türkiye’deki Yag lu, S.O., ıs¸ların Kararlı Izotop Içeriklerini Sayın, M., Eyüpog
_ ruların Belirlenmesi. 2. Ulusal Hidrolojide Izotop Kullanarak Yerel Meteorik Dog _ Tekniklerinin Kullanılması Sempozyumu, Izmir, pp. 323e344. Schoeller, H., 1967. Geochemistry of Groundwater. An International Guide for Research and Practice, vol. 15. UNESCO, pp. 1e18. Seleem, E.G., 2014. Hydrochemistry of shallow groundwater around Quesna industrial city, Egypt. J. Am. Sci. 10 (9), 90e97. Sharma, P., Sharma, H.P., 2011. Groundwater quality assessment of Pachim Nalbari block of Nabari district Assam based on major ion chemistry. Int. J. chemTech Res. 3 (4), 1914e1917. Todd, D.K., 1980. Groundwater Hydrology, 2rd ed. John Wiley and Sons, New York. _ TSE-266, 2005. Içme Suları Standardı. Türk Standartları Enstitüsü, vol. 266. Baskı TSE, TS, Ankara, pp. 1e25. UNEP/WHO, 1996. Water Quality Monitoring - a Practical Guide to the Design and Implementation of Freshwater Quality Studies and Monitoring Programmes. Published on behalf of United Nations Environment Programme and the World Health Organization. Weissmann, G.S., Zhang, Y., LaBolle, E.M., Fogg, G.E., 2002. Dispersion of Groundwater Age in an Alluvial Aquifer System, vol. 38. WRR, California, USA, pp. 1198e1211. WHO, 2008. Guidelines to Drinking Water Quality. World Health Organisation, Geneva, pp. 289e405.
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Journal of African Earth Sciences journal homepage: www.elsevier.com/locate/jafrearsci
Assessment of hydrogeochemistry and environmental isotopes of surface and groundwaters in the Kütahya Plain, Turkey ur Erdem Dokuz b, Mehmet Çelik c Berihu Abadi Berhe a, *, 1, Ug an, Ankara, Turkey Ankara University, Graduate School of Applied Science, Geological Engineering Dept., 06100, Tandog € de, Turkey Omer Halisdemir University, Faculty of Engineering, Geological Engineering Dept., 51240, Nig c €lbas¸ı, Ankara, Turkey Ankara University, Faculty of Engineering, Geological Engineering Dept., 50th Year Campus, 06830, Go a
b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 31 January 2017 Received in revised form 20 May 2017 Accepted 22 June 2017 Available online 22 June 2017
The aim of the present work is to determine the geochemical processes that control the nature of the groundwater and assess the quality of water for drinking and public health purposes. Surface and groundwater samples of Kütahya plain were analyzed for their physio-chemical and environmental isotope properties. The relative concentrations of the water ions were found to occur in the order of 2Ca2þ>Mg2þ>(Kþ þ Naþ) and HCO 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 d2H and 9.25 d18O. Tritium activities in groundwater from the wells ranged from 1.00 to 8.38 TU with a mean value of 4.37 TU. The impact of agricultural practices and poor sanitation conditions is indicated by þ þ 2þ the positive correlation between Kþ - NO ions 3 , K - NO2 and HCO3 - Cl ions as well as Na and Mg with SO2 4 ion. The groundwater quality of Kütahya plain is influenced by various natural and anthropogenic factors. © 2017 Elsevier Ltd. All rights reserved.
Keywords: Hydrogeochemistry Water quality Water types Isotopes Geochemical evolution Kütahya plain
1. Introduction Groundwater is one of the most crucial resources for human life. The quality of water depends upon the geological environment, natural movement and human activities. Nowadays, basic demands for fresh water are for the purpose of irrigation, household and municipal water use, and industrial uses (UNEP/WHO, 1996). The present study area, Kütahya plain and its catchment lies between 225000 and 268000E longitude and 4345000e4380000N latitude with an area of around 93 km2 and its total catchment covers about 550 km2. It is crossed by two perennial rivers called the Felent and the Porsuk Rivers (Fig. 1). According to the data recorded at Kütahya Meteorological Station between the years 1975 and 2011, the mean annual precipitation and air temperature are 543.85 mm and 10.81 C, respectively. € prüo €ren plain and The study area is located in downstream of Ko
* Corresponding author. E-mail address: [email protected] (B. Abadi Berhe). 1 Wollo University, College of Natural Science, Department of Geology, 1145, Dessie, Ethiopia. http://dx.doi.org/10.1016/j.jafrearsci.2017.06.015 1464-343X/© 2017 Elsevier Ltd. All rights reserved.
upstream of Porsuk dam the water of which is used by people living in Eskis¸ehir and Kütahya for both irrigation and domestic purposes. Heavy metal concentrations in soil samples and leaves of trees and € prüo € ren basin have relatively higher conherbaceous plants in Ko centrations (Arık and Yaldız, 2010).The waters form spring, rivers and groundwaters of Kütahya plain contain As, Pb, and U concentrations and the As concentration in all waters is above the maximum contaminant level (Kavaf and Nalbantcilar, 2007). In the study area, people of this district and surrounding villages are the primary users of groundwater for drinking, industrial and irrigation and the surface water irrigation for purposes. The area is one of the Turkey's regions experiencing an exponential growth of intensive agriculture and industrial activity. The interactions between agricultural irrigation, surface water and groundwater resources are always very close. The agricultural activities and industrial establishments in Kütahya city such as sugar factories, nitrogen and magnesium factories and leather industries are responsible for disposing of treated and untreated effluents in the natural drainage system of the Felent and the Porsuk rivers. The most common nitrogen fertilizer currently used in all the agricultural lands of the Kütahya plain are urea (CO(NH2)2), DAP
B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240
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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
((NH4)2HPO4), ammonium sulphate ((NH4)2SO4), ammonium nitrate (NH4NO3), magnesium sulphate (MgSO4), potassium nitrate (KNO3) and potassium sulphate (K2SO4) (KÇS¸M, 2012). Hydrogeochemical processes such as dissolution, precipitation, ion exchange and the residence time along the flow path govern chemical compositions of groundwater (Martinez and Bocanegra, 2002). The main objective of the present work is to investigate the geochemical processes that control the nature of the groundwater and assess the quality of water for drinking and public health purposes. The study was performed using hydrochemical and environmental isotopic data of oxygen-18, deuterium and tritium.
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 field using standard field equipment (Multi 350i multiparameter). Water samples were filtered using 0.45-mm disposable capsule filter 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 fitting covers. The analysis was done using DIONEX LC25, ICS-1000 High-Performance Ion Chromatography system, YSI MPS 556 Multi-probe system, and 2Automatic acid titration burette (for HCO 3 and CO3 ) at Hacettepe University Water Chemistry Laboratory in Ankara, Turkey. The American Public Health Association (APHA, 1989) standard Methods were used for the Examination of Water and Wastewater. The stable isotopic analyses were performed at the Laboratory of the international research and application center for karst water resources in Hacettepe University, Ankara, Turkey (Berhe et al., 2014). The hydrochemical results were plotted on Piper diagram using AquaChem 5.1 software. Statistical descriptive analysis and correlation between different parameters of waters were done by SPSS software package version 16.0. Mineral saturation index of all water 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 ürler Complexes, SabSarıcasu Formation, Arıkaya Formation, Çüg €ren Formation uncupınarı Formation, Emet Formation, Parmako and Alluvials (Fig. 2). The basement rocks are comprised of meta€g ürler Complexes rocks (DSI, 1981; morphic schists, Marbles and Ço € DSI, 2003; Ozburan, 2009). Sarıcasu Formation of Paleozoic age is composed of schists, calcschist, quartz schist and crystallized limestone and overlain by Arıkaya Formation of Upper Permian-Lower Triassic age, Marble. Crystalline limestones unconformably overlie the Çayca Tuf and at the top, and it is unconformably covered by Pleistocene age of €ren Formation and alluvials. The Quaternary alluvial, Parmako which covers the plain, comprises fluviatile pebble, gravel, sand, and silt, is widely distributed in this plain, and has a maximum depth of 100 m. The gravely and sandy horizons in Kütahya plain form one of the best aquifers. The mean hydraulic conductivity (K) and transmissivity (T) obtained from analysis of pumping test and recovery data for this aquifer were 44.42 m/day and 213.48 m2/day, € ren Forrespectively. The sandstone and gravelstone of Parmako mation are permeable material and its mean value of hydraulic
The physicochemical parameters of surface water samples collected from the Felent and Porsuk Rivers and groundwaters in December 2013 were compiled in Table 1. The average water temperature, pH and electrical conductivity values of the surface waters were 13.2 C, 8.43 and 907.25 mS/cm whereas groundwater samples had 13.21 C, 8.18 and 1006.90 mS/cm, respectively. The pH values of all waters used in the study area elaborate a trend of alkaline chemical reaction within the groundwater system (Tables 1 and 2). Minimum, maximum and mean concentrations of ions present in surface and groundwater from the study area are presented in Tables 1 and 2. The relative concentrations of the surface and groundwater ions occur in the order of Ca2þ>Mg2þ>(Kþ þ Naþ) and 2 HCO 3 >SO4 >Cl . The predominant cations of surface waters were Ca2þ and Mg2þ with a mean value of ion concentration 96.42 and 38.68 mg/l, respectively, whereas HCO 3 with a mean value of 441.21 mg/l was a dominant anion. Among the major cations of groundwater of the plain same as surface waters Ca2þ and Mg2þ were again predominates and their average concentration were 92.57 and 52.82 mg/l respectively. Among the major anions, HCO 3 with an average concentration of 414.45 mg/l was the dominant ion
Fig. 1. Location of study area and sampling points.
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€ Fig. 2. Geological map of the study area (modified from DSI, 1981; 2003; Ozburan, 2009).
(Tables 1 and 2, and Fig. 4). 5. Hydrochemical facies Piper diagram is the most convenient way for plotting the results of multiple analyses on the same graph, which may disclose grouping of certain samples and show different hydrochemical facies or origin of groundwater (Piper, 1944). By using the Piper diagram, the surface and groundwaters of the study area can be categorized into the following groups: Ca-Mg-HCO3 (66.67%), MgCa-HCO3 (18.52%), Ca-HCO3 (7.41%), Mg-Ca-SO4-HCO3 (3.7%) and Mg-Ca-HCO3-SO4 (3.7%), revealing that the Ca-Mg-HCO3 water type 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 are from the same origin. 6. Drinking water quality The analytical physio-chemical parameters of groundwater were compared with the standard guideline values as recommended by the Turkish Standards Institution (TSE-266, 2005) and World Health Organization (WHO, 2008) for drinking and public health purposes (Table 2). Temperature, pH (except 3 samples according to WHO), and the concentration of ions, such as Naþ, Ca2þ, PO34 , F and Cl in the investigated groundwater samples were within the maximum permissible limits TSE-266 and WHO standards. Only one of the groundwater samples exceeded the EC limit of TSE-266 standard, but two samples according to WHO. Furthermore, 23.8% of the samples exceeded the hardness permissible limit of WHO. The concentration of Mg2þ shows that 28.3% and 4.7% of the samples exceeded the acceptable limits of TSE-266 and WHO, respectively. Although Kþ concentration of the groundwater is very low as
compared to Ca2þ and Mg2þ ions, 3 water samples were found out above allowable TSE-266 limits. Nevertheless, none of them were above WHO limits (Table 2). The nitrate concentration value obtained from two water samples was higher than that of TSE-266 and WHO limits for drinking water. The results of nitrite concentration of study area depict that 4 water samples exceeded the allowable limits of TSE-266. However, comparing with permissible limits of WHO all water samples are under the limits. NHþ 4 concentration of water samples disclosed that about 33.3% and 4.7% were above the permissible limits of TSE266 and WHO, respectively (Table 2). The concentration of SO24 in groundwater reveals that only one water sample exceeded the standard allowable limits of TSE-266 and WHO for SO24 (Table 2). 7. Composition diagrams The most acceptable method to classify and compare intermixing fresh and saline waters based on ionic composition is by plotting the chemical data on a composition diagrams. Mixing lines indicate the mix of contaminated and fresh end members in various proportions (Mazor, 2004). The surface and groundwaters vary notably in their chemical concentrations, the data plot on straight lines is an indication for a positive correlation between Ca2þ, Mg2þ, 2 Naþ, HCO 3 , SO4 and Cl with the total dissolved ion (TDI) (Fig. 5). Fig. 5a and d shows that the line extrapolating to values on the Ca2þ and HCO 3 axis indicates that both intermixing waters contain a significant concentration of Ca2þ and HCO 3 . In Fig. 5b, c, e and f, the line extrapolates to point in the TDI line, showing the fresh end member contains a significant concentration of ions other than Mg2þ, Naþ, SO24 and Cl . 8. Correlation coefficient analysis The correlation coefficient is a vital method in building the
B. Abadi Berhe et al. / Journal of African Earth Sciences 134 (2017) 230e240
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Fig. 3. Hydrogeological cross sections. Lines of section indicated on Fig. 2.
relationship between two variables (Anandakumar et al., 2009). Pairs that have high positive correlation show the dependency of one parameter on the other (Sharma and Sharma, 2011). Correlations between major ions in surface and groundwater within the study area were carried out using Pearson's correlation analysis in SPSS 16.0 program (Table 3). Correlation coefficients of major and some minor ions were computed using values of concentrations of the different ions in mg/l. The high correlation co 2þ efficient between Naþ- Cl, Mg2þ - HCO 3 and Ca - HCO3 ions was observed. Therefore, it can be concluded that for most of the water 2þ samples of the area Naþ and Cl, Mg2þ and HCO and HCO 3 , Ca 3 have originated from the common source. Perfect correlation be2 tween EC and major ions (Ca2þ, Mg2þ, Naþ, HCO 3 , Cl and SO4 ) indicates that EC is a measure of major ion concentration in water samples. There is a very high positive correlation between Kþ- NO 3 2 2 2 (r ¼ 0.97), Kþ- NO 2 (r ¼ 0.84) and HCO3 Cl (r ¼ 0.83) ions as
well as Naþ and Mgþ2 ions with SO24 ion, indicating the anthropogenic impact from agricultural practices and poor sanitation conditions. Other moderately inter-relationships exist as shown in Table 3. 9. Molar ratio between major ions Naþ/Cl¡ relations: When halite dissolution is accountable for sodium, the Naþ/Cl molar ratio is nearly one, whereas a ratio >1, it is typically deduced that Naþ is released from a silicate weathering reaction (Meybeck, 1987). In the current study area, Naþ/Cl molar ratio generally ranges from 0.69 to 6.36 with an average of 1.78. In a plot of Naþ against Cl (Fig. 6), most of the samples lie above 1:1 trend line showing excess Naþ. This excess Naþ may be the result of silicate weathering reaction process or anthropogenic activities. Ca2þ/Mg2þ relations: In the study area, the dominant cations were calcium and magnesium, while bicarbonate was dominant
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Table 1 Statistical descriptive of physicochemical of surface waters (n ¼ 6) of the study area. Parameters
Units
Min
Max
Mean
St.dev
Ph T EC Liþ NHþ 4 Kþ þ Na Mg2þ Ca2þ PO34 Br F NO 2 NO 3 Cl SO24 HCO 3 TDI
e C mS/cm mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l meq/l
7.70 10.30 613 0.00 0.00 2.61 9.74 21.32 81.02 0.00 0.02 0.08 0.17 0.19 2.36 9.05 337.57 12.26
9.67 15.20 1111 0.02 13.14 30.51 31.97 63.95 119.66 0.69 0.17 0.31 1.31 19.9 31.4 90.03 574.47 22.22
8.43 13.20 907.25 0.01 2.77 9.19 22.05 38.68 96.42 0.23 0.07 0.21 0.50 6.01 19.65 42.73 441.21 18.15
0.74 1.89 231.92 0.01 5.23 10.59 9.78 19.05 15.59 0.27 0.05 0.08 0.43 7.51 12.1 33.42 86.94 4.64
et al., 1998; Elango et al., 2003). In the study area, the Ca2þ/Mg2þ ratio of the surface and groundwater samples ranged between 0.25 and 12.86 and its mean value was 1.88 (Fig. 7). About 77.8% samples had a ratio <2 disclosing the dissolution of calcite, whereas the rest 22.2% samples had a ratio >2, which indicates the effect of silicate minerals. 2þ (Ca2þ þ Mg2þ)/HCO¡ 3 relations: Appraisal of the slopes of Ca 2þ and Mg versus HCO3 gives crucial information about the sources of Ca2þ and Mg2þ in groundwater (Richter and Kreitler, 1993). Dissolution of silicate and oxidation of organic matter may have produced the excess HCO3- in the groundwater (Seleem, 2014). In the study area, a plot of Ca2þ þ Mg2þ versus HCO3 shows that about 96.2% of sampled waters plot below the 1:1 aquiline (Fig. 8). This indicates a deficiency of Ca2þ þ Mg2þ relative to HCO3-. Therefore, some HCO 3 is also coming from processes other than calcite or dolomite dissolution, or the Ca2þ and Mg2þ are lost in the cation exchange reactions and it might have been balanced by Naþ and Kþ or supplied by silicate weathering.
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
Ph T EC Hardness Liþ NHþ 4 Kþ Naþ Mg2þ Ca2þ PO34 Br F NO 2 NO 3 Cl 2SO4 HCO 3 TDI
e C mS/cm mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l meq/l
Groundwater (n ¼ 21)
TSE (266) 2005
WHO (2008)
Min
Max
Mean
St.dev
Maximum permissible No. of samples > standard limit Maximum permissible No. of samples > standard limit
7.49 8.50 483.00 239.16 0.00 0.00 0.60 2.27 6.89 21.93 0.00 0.00 0.00 0.11 0.07 1.78 2.73 275.39 9.67
9.11 17.1 3135 1363.09 0.09 3.10 158.99 105.54 237.91 154.3 1.39 0.47 0.43 2.94 225.43 173.94 649.43 731.41 62.70
8.18 13.21 1006.9 448.23 0.02 0.61 17.18 22.59 52.82 92.57 0.23 0.09 0.21 0.48 28.35 29.62 76.91 414.45 20.14
0.43 1.78 647.11 251.13 0.02 0.72 42.69 27.12 48.56 35.45 0.37 0.11 0.13 0.63 57.45 42.79 142.7 119.22 12.94
6.5e9.2 25 2000 e e 0.05e0.5 12 175 50 200 5 e 1.5 0.1 50 600 250 e
None None 2 e e 7 3 None 5 None None e None 16 2 None 1 e
6.5e8.5 30 1500 500 e 1.5 50 200 150 250 6.5 e 1.5 3 50 250 250 e
3 None 2 5 e 1 None None 1 None None e None None 2 None 1 e
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 ¼ 2:5 Ca2þ þ 4:1 Mg2þ
Fig. 4. Piper diagrams of surface and groundwaters in Kütahya Plain.
anion in groundwater. The points plotted on the line Ca2þ/Mg2þ ¼ 1 indicate waters controlled by dolomite dissolution while the Ca2þ/ Mg2þ ratio ranging from 1 to 2 characterizes the dissolution of calcite (Maya and Loucks, 1995). In natural waters, Ca2þ/Mg2þ ratio greater than 2 is mainly due to the dissolution of silicate minerals, which contribute calcium and magnesium in groundwater (Katz
(1)
Where TH, Ca2þ and Mg2þconcentrations are all in mg/l (Todd, 1980). 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) classification, 18.5% of the water samples are hard, while 81.5% falls under very hard category (Tables 4 and 5). 11. Ion exchange Chloro Alkaline Indices (CAI): Schoeller (1967) has formulated a formula used to be known as the ion exchange between the
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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 ¼ 0), undersaturated (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 undersaturated with respect to sulphate minerals (anhydrite and gypsum) (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
Fig. 5. A composition diagram of surface and groundwater of Kütahya Plain. Concentrations are given in meq/l.
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 represented by the equation: d2H ¼ 8d18O þ 10 (Craig, 1961). Moreover, the Local Meteoric Line established for Isparta (ILMWL) is
Table 3 Correlation coefficients between major ions in surface and groundwaters of study area. Parameter
pH
EC
Liþ
NHþ 4
Kþ
Naþ
Mg2þ
Ca2þ
PO34
Br
F
NO 2
NO 3
Cl
SO24
HCO 3
pH EC Liþ NHþ 4 Kþ þ Na Mg2þ Ca2þ PO34 Br F NO 2 NO 3 Cl 2SO4 HCO 3
1 0.28 0.08 0.23 0.11 0.27 0.31 0.15 0.07 0.29 0.27 0.07 0.12 0.29 0.33 0.16
1 0.45 0.10 0.55 0.96 0.92 0.71 0.26 0.93 0.53 0.50 0.49 0.99 0.92 0.90
1 0.04 0.87 0.54 0.22 0.36 0.78 0.36 0.45 0.68 0.84 0.44 0.22 0.39
1 0.08 0.22 0.06 0.02 0.12 0.13 0.14 0.18 0.16 0.13 0.12 0.19
1 0.59 0.32 0.41 0.62 0.41 0.32 0.84 0.97 0.52 0.24 0.55
1 0.85 0.66 0.30 0.93 0.64 0.47 0.51 0.97 0.89 0.83
1 0.43 0.07 0.88 0.49 0.33 0.27 0.92 0.95 0.76
1 0.25 0.62 0.27 0.37 0.36 0.65 0.57 0.79
1 0.16 0.36 0.49 0.59 0.21 0.05 0.31
1 0.62 0.26 0.31 0.95 0.92 0.79
1 0.21 0.26 0.56 0.52 0.42
1 0.84 0.45 0.21 0.54
1 0.47 0.19 0.45
1 0.94 0.83
1 0.72
1
Strong correlations between two parameters are showed in bold numbers.
groundwater and its surroundings during residence or travelling in the aquifer (eq (2) and (3)). Positive CAI indicates the exchange of Naþ and K from the water with Mg2þ and Ca2þ of the rocks and is negative when there is an exchange of Mg2þ and Ca2þ of the water with Naþ and Kþ of the rocks (Nagaraju et al., 2006; Çelik et al., 2008).
CAI1 ¼
CAI2 ¼
Cl Naþ þ Kþ Cl
Cl Naþ þ Kþ
(2)
SO2 þ HCO 4 3 þ CO3 þ NO3
(3)
According to Table 5, 92.6% of the samples from the study area showed negative ratios indicating an indirect base-exchange reaction. During this process, the host rocks were not considered to be the principal sources of dissolved solids in the water and reflected the dominance of direct ion-exchange of Naþ/Kþ in the water with Mg2þ/Ca2þ in the host rock.
€ 2005). Variations in the d2H ¼ 8d18O þ 12.16 (Sayın and EyüpogluO, stable-isotope signature of groundwater are due to natural variations in the isotopic composition of rainfall such as mixing with pre-existing waters, and evaporation during percolation through the soil and/or the unsaturated zone (Kendall and McDonnell, 1998). 19 water samples for stable isotope analyses (oxygen and hydrogen isotopes) were collected during December 2013 from surface water, shallow and deep groundwater through December 2013 (Table 6) and were plotted as can be seen in Fig. 9. The measured d2H and d18O values of surface water samples collected during this study range from 67.54 to 61.50 and 9.80 to 8.25, respectively. On the other hand, groundwaters range from 72.23 to 61.27 and from 10.45 to 8.43, respectively. The result is disclosing that the surface and groundwaters are isotopically depleted (Table 6). The groundwaters have a mean isotopic composition of 67.32 (d2H) and 9.72 (d18O) and these values are comparatively lower than surface waters 64.64 (d2H) and 9.25 (d18O), thus surface waters are more positive than groundwaters
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Na+ (mmol)
5 4
ine
l 1:1
3 2 1 0 0
1
2
3
4
5
6
Cl- (mmol) Fig. 6. Naþ versus Clgraph.
Table 4 Hardness of waters.
Fig. 7. Ca2þ/Mg2þ ratio graph of water samples.
Hardness
Water classification
% Result of this study
0e75 75e150 150e300 >300
Soft Moderately hard Hard Very hard
e e 18.5 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 undergone some evaporation before or during their underground transportation system (Fig. 9). Clark and Fritz (1997) established d18O-Cl- relationship graph 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 ¼ 0.076) (Fig. 10). This implies that even if evaporation occurs, its impact upon the salinization of groundwater may be insignificant.
13.2. Tritium
Fig. 8. Ca2þ þ Mg2þ against HCO 3 graph.
revealing evaporation effect on surface waters. However, they are generally similar and are plotted on the same area on d2H - d18O, indicating that they have originated from the same source, which supports the Piper graph. The diagram d2H - d18O shows that the surface and groundwater plot on/or is close those of ILMWL and the GMWL suggesting their
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. 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 of 4.37 TU (Table 6). The tritium contents in shallow groundwater ranged from 2.52 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, indicating the presence of relatively old groundwater in this part (Fig. 11a). The graph of tritium content of groundwater and its measured
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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 Surface waters (n ¼ 6)
Groundwaters (n ¼ 21)
SIcalcite
SIaragonite
SIdolomite
SIgypsum
SIanhydrite
TH
CAI1
CAI2
PÇ-3 PÇP PÇÇ FÇ-1 FÇ-2 FÇ-3 Min Max Mean St.Dev SKK OKK SÇ AKÇ ÇÇ BST-1 BST-2 AT-1 _ IYKT-1
1.09 1.38 0.67 2.24 1.62 0.94 0.67 2.24 1.32 0.56 1.38 0.35 0.45 1.12 0.93 0.79 0.60 1.10 2.12
0.94 1.23 0.51 2.08 1.46 0.79 0.51 2.08 1.17 0.56 1.22 0.19 0.30 0.96 0.78 0.64 0.44 0.95 1.96
1.78 2.37 1.03 4.44 3.17 1.61 1.03 4.44 2.4 1.24 2.47 1.27 0.59 1.99 1.81 1.43 1.31 2.35 4.20
2.58 2.17 2.09 1.77 1.63 2.15 2.58 1.63 2.07 0.33 2.83 2.87 2.28 2.00 2.53 2.46 2.47 1.49 1.33
2.83 2.42 2.34 2.03 1.89 2.40 2.83 1.89 2.32 0.33 3.09 3.12 2.53 2.25 2.78 2.72 2.72 1.74 1.58
295.49 306.52 316.37 510.03 519.3 462.33 295.49 519.3 401.67 106.64 239.16 272.36 316.37 377.41 317.46 363.13 433.97 729.76 719.96
6.37 1.78 1.48 0.50 0.37 1.89 6.37 0.37 2.07 2.2 1.41 0.72 2.20 0.99 1.50 0.25 1.30 1.65 1.45
0.07 0.05 0.12 0.04 0.03 0.14 0.14 0.03 0.08 0.05 0.02 0.01 0.05 0.06 0.04 0.01 0.02 0.26 0.23
ZKT-1 KOY-1 BK-A _ IG-1
1.15 0.62 1.15 0.89
1.00 0.47 0.99 0.74
1.16 1.03 2.20 1.81
1.64 2.11 2.47 1.32
1.90 2.36 2.73 1.57
393.27 416.6 361.75 602.17
1.31 0.23 0.15 0.17
0.06 0.01 0.01 0.03
_ IG-2 _ IG-3 KOYM K-1 K-2 € PO-1
1.39
1.24
2.85
1.94
2.19
416.05
0.93
0.06
1.99
1.84
4.39
0.92
1.17
1363.09
0.02
0.00
0.20 0.75 0.80 1.06
0.05 0.60 0.65 0.91
0.91 1.12 1.51 2.09
2.42 1.93 1.85 2.77
2.67 2.18 2.1 3.02
521.51 310.93 358.25 247.63
0.06 0.44 0.79 3.26
0.01 0.05 0.07 0.1
SKÇK OK Kuyu Min Max Mean St.Dev
1.46 1.11 0.2 2.12 1.02 0.48
1.31 0.96 0.05 1.96 0.87 0.48
2.14 2.01 0.59 4.39 1.94 0.97
2.4 3.21 3.21 0.92 2.15 0.59
2.65 3.46 3.46 1.17 2.41 0.59
400.12 251.84 239.16 1363.09 448.23 251.13
0.53 0.67 3.26 0.15 0.94 0.82
0.01 0.01 0.26 0.01 0.05 0.07
Table 6 Measured values of environmental isotopes of the study area.
d2H (‰)
d18O (‰)
3
PÇ-3 PÇP FÇ-1 FÇ-3 Min Max Mean St.Dev SKK OKK SÇ AKÇ ÇÇ BST-2 AT-1 _ IYKT-1
65.98 67.54 63.53 61.50 67.54 61.50 64.64 2.66 e 68.68 72.23 65.65 67.78 68.72 68.14 70.00
9.57 9.80 9.37 8.25 9.80 8.25 9.25 0.69 e 10.45 10.36 9.40 9.56 9.89 9.51 9.99
e e e e
7.39 6.26 e 4.22 2.52 8.38 3.38 3.11
ZKT-1 BK-A _ IG-2
69.13 65.71 65.06
10.35 10.16 9.09
3.76 6.47 3.08
KOYM K-1 € PO-1
64.75 65.42 61.27
9.74 9.05 8.43
e 1.66 1.00
SKÇK OK Kuyu Min Max Mean St.Dev
68.54 68.67 72.23 61.27 67.32 2.67
9.61 10.19 10.45 8.43 9.72 0.57
4.44 5.52 1.00 8.38 4.37 2.17
Sample No Surface waters
Groundwaters
H (TU)
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Fig. 9. Plot of d2H versus d18O of study area.
Fig. 10. Graph of d18O(‰) versus Cl of groundwater in Kütahya 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 Mg2þ, Kþ, NO 3, 2þ NO 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 Kütahya plain. Surface waters show more positive d2H and d18O than groundwaters 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. Acknowledgment
Fig. 11. EC versus 3H (a) and d18O versus 3H(b) graph of the study area.
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 flow direction of the area. 14. Conclusion The predominant cations and anions of surface and groundwater are Ca2þ and Mg2þ, and HCO 3 respectively. Ca-Mg-HCO3 followed by Mg-Ca-HCO3 was the most dominant hydrochemical facies in the study area. In the study area, water chemistry is primarily controlled by water-rock interactions. Natural dissolution of carbonate rock (reaction between water and the limestone rocks of Emet Formation) was the primary source of Ca2þ and HCO 3 in groundwater. The Mg2þ ion is resulted from the water-rock interaction in ophiolitic rocks of the study area. Perfect correlation between EC and major ions indicates that EC is a measure of major ion concentration in water samples. Excess Naþ in Naþ versus Cl graph could result from silicate weathering reaction process or an anthropogenic activity. The ratio of Ca2þ/Mg2þ of the surface and groundwater samples disclosing the dissolution of calcite was dominant. About 81.5% waters of the study area fall under very hard water category. Chloro Alkaline Indices of the water reflects the dominance of direct ion-exchange of Naþ/Kþ in the water with Ca2þ/Mg2þ in the host rock. Therefore, it can be concluded that the geochemical process in the area that influenced the chemical composition of the water sources is the dissolution of carbonate minerals, which contributes the Ca2þ, Mg2þ, and HCO 3 to the groundwater. In addition to the natural water-rock interaction, human activities are also the main causes to increase the concentrations of some elements in groundwater. The positive correlation between þ 2þ 2Kþ- NO 3 , K - NO2 , Mg -SO4 ions could be resulted from the usage of excess amount of ammonium sulphate, ammonium nitrate, magnesium sulphate, potassium nitrate and potassium sulphate during agricultural practices. The presence of excess amount of ammonia, nitrate, nitrite and magnesium result from fertilizers in the soil making it, even more,
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