Environ Earth Sci DOI 10.1007/s12665-013-3036-1
ORIGINAL ARTICLE
Groundwater quality assessment and its suitability in C ¸ eltikc¸i plain (Burdur/Turkey) ¨ zdemir Ays¸ en Davraz • Arkın O
Received: 21 February 2013 / Accepted: 26 December 2013 Ó Springer-Verlag Berlin Heidelberg 2014
Abstract The C ¸ eltikc¸i (Burdur) plain is located in the southwest of Turkey and is a semi-closed basin. Groundwater is densely used as drinking, irrigation and domestic water in the plain. Hydrogeochemical processes controlling groundwater chemistry and geochemical assessment of groundwater were investigated in the C ¸ eltikc¸i (Burdur/ Turkey) plain. In this study, groundwater samples for two seasons were analyzed and major ion chemistry of groundwater was researched to understand the groundwater geochemistry. Two major hydrochemical facies (Ca–HCO3 and Ca–Mg–HCO3) were determined in the area. Various graphical plots and multivariate statistical analysis were used for identifying the occurrence of different geochemical processes. In the study area, weathering is one of the key geochemical processes which controlled the solute concentration in groundwater. Chemical indexes such as sodium adsorption ratio, %Na, residual sodium carbonate, magnesium hazard and permeability index were calculated and results show that groundwater is suitable for irrigation purpose except for permeability index values. Concentrations of Mn, NO3 and total hardness exceed the prescribed limits of WHO and are the major limiting parameters of groundwater use for potable and domestic purposes. Keywords Groundwater quality Hydrogeochemical processes C ¸ eltikc¸i plain Turkey
¨ zdemir A. Davraz (&) A. O Department of Geology Engineering, Faculty of Engineering, Su¨leyman Demirel University, Isparta, Turkey e-mail:
[email protected];
[email protected]
Introduction Groundwater is the primary source of water for domestic, agricultural and industrial uses in many countries. As groundwater moves along its flow path from recharge to discharge areas, a variety of hydrogeochemical processes alters its chemical composition. The chemistry of groundwater is an important factor controlling its use for domestic, irrigation and industrial purposes. Groundwater chemistry depends on a number of factors such as general geology, degree of chemical weathering of the various rock types, quality of recharge water, and influence of external pollution agencies like effluents from agricultural return flow, industrial and domestic activities (Srinivasamoorthy et al. 2012; Ekwere and Edet 2012; Aghazadeh and Mogaddam 2010). Such factors and their interactions result in a complex groundwater quality (Aghazadeh and Mogaddam 2011; Singh et al. 2011; Ayenew et al. 2008; Domenico and Schwartz 1990; Giridharan et al. 2008; Kumar et al. 2006). Groundwater chemistry could reveal important information of the suitability of groundwater for domestic, industrial and agricultural purposes. Despite the importance of groundwater, little is known about the natural phenomenon that governs its chemical composition or the anthropogenic factors that affect its quality (Garcia et al. 2001). Understanding the chemical composition of groundwater, therefore, will aid in the development and management of groundwater for various uses. Over the last few decades, economic development associated with rapid growth in population and urbanization has brought in significant changes in land use, resulting in more demand of water for agriculture and domestic activities. Therefore, groundwater resources are at risk due to overexploitation and pollution in many parts of the
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world. Factors affecting the quality of groundwater can be classified as having either natural or anthropogenic sources. Important sources of natural groundwater pollution in Turkey include geogenic factors, seawater intrusion and geothermal fluids. The major sources of anthropogenic groundwater contamination in Turkey are agricultural activities, industrial waste and on-site septic tank systems (Baba and Tayfur 2011). The increase of fluoride related to water–rock interaction is determined by several researches in Turkey (Davraz et al. 2008; C ¸ oban et al. 2001; Oruc and Vicil 2001; Fidancı et al. 1994; Fidancı 1997; Sendil and Baysu 1973; Oruc 1977; Uslu 1982; Baba and Ayyıldız 2006; Baba and Tayfur 2011). The fluoride contents of springs discharged from volcanic rocks are between 3.71 and 5.62 mg/l in Isparta city (Davraz et al. 2008). Fluoride is predominantly supplied by dissolution of fluoride within the fluormicas of volcanics during the circulation of water (C¸oban et al. 2001). Fluoride concentrations of waters have shown variations for dry and rainy seasons depending on the degree of interaction between groundwater and volcanic rocks (Davraz et al. 2008). Analyses of surface and groundwater samples from Gu¨llu¨ village (Us¸ ak) showed fluoride concentrations between 0.7 and 2 mg/l (Oruc and Vicil 2001). By examining drinking water sources around the villages of Beylikova–Kızılcao¨ren (Eskis¸ ehir), Uslu (1982) and Fidancı et al. (1994) found fluoride concentrations to be around 3.9–4.8 and 2.0–9.2 mg/l, respectively. Kaman–Bayındır (Kırs¸ ehir) is one of the famous regions for fluoride formation, and groundwater in the region contains approximately 2.6 mg/l of fluoride (Fidancı 1997). According to another research, fluoride concentrations in groundwater related to hydrothermal fluorite mineralizations for dry and wet periods are 0.17–4.86 and 0.23–3.55 mg/l, respectively, in Kaman (Kırs¸ ehir) region ¨ zmen et al. 2011). In addition, fluoride contamination in (O groundwater has also been observed in the Dog˘ubeyazıt (Ag˘rı), Muradiye (Van), Habiller (Edirne) Denizli and Aydın regions (S¸ endil and Baysu 1973; Oruc 1977; Uslu 1982; Baba and Ayyıldız 2006; Baba and Tayfur 2011). Arsenic pollution has also become an important topic in the agenda of Turkey. Groundwater sources in the provinces of Aksaray, Afyon, I˙zmir, Manisa, Nevs¸ ehir, Kırklareli, Ku¨tahya, Balıkesir, Van and Sivas have a high concentration of arsenic whose enrichment in groundwater is of global concern. Weathering and dissolution of arsenic minerals, water–rock interactions, and geothermal processes cause groundwaters to be enriched in arsenic (Baba and Tayfur 2011). According to some researches, the groundwater arsenic contamination in Western Anatolia mainly originates from highly weathered Menderes metamorphic rocks, sulfide minerals, boron as well as coal and colemanite mines (C¸olak et al. 2003; Gemici and Oyman
123
2003; Gunduz et al. 2009, 2010; S¸ ims¸ ek 2013). Arsenic is one of the major pollutants in Bigadic¸ and showed high spatial variation ranging from 33 to 911 lg/l in groundwater samples. Arsenic values increased close to the Simav and Gu¨nevi mines (located near Bigadic¸), reaching 305 lg/l, and decreased to the south of Bigadic¸ area (Gemici et al. 2008) and also in the Simav plain, reaching 561 lg/l (Gu¨ndu¨z 2009; Gu¨ndu¨z et al. 2009). The hydrochemical studies of the area surrounding the Hisarcık (Emet-Ku¨tahya) colemanite mine show extremely high arsenic contamination in groundwater between 0.07 and 7.754 mg/l (C ¸ olak et al. 2003). In the S¸arkıs¸ la plain (Sivas), the water–rock interaction processes in sulfide-bearing rocks were responsible for the remarkably high groundwater arsenic contamination. Groundwater arsenic concentration ranged between 0.5 g/l and 345 lg/l in the area (S¸ims¸ ek 2013). Due to high B concentrations of thermal waters, environmental problems in ground and surface waters in some agricultural areas of western Anatolia have been observed. Boron concentrations of thermal waters from western Turkey have a wide range of 1–63 mg/l. The metamorphic Menderes Massif mainly hosts the thermal waters in the western Anatolia. Although gneisses and schists generally have low boron contents, sericite, illite and tourmaline minerals that are abundant in the Menderes Massif rocks are considered to be one of the reasons for the high boron additions to thermal waters by water–rock interactions. Cold groundwaters contaminated with boron from geothermal fluids have higher values (such as in Bu¨yu¨k Menderes, Gediz grabens and Balc¸ova plains). Although the B content of groundwater is \1 mg/l in a great part of the Gediz plain in some areas this value exceeds 3 mg/l (Gemici and Tarcan 2002). The impact of geothermal water on ground and surface waters has been determined in many parts of Turkey ¨ zler 2000; Aksoy (Dog˘du and Bayarı 2005; Afs¸ in 1997; O et al. 2009; Aksever 2011). Thermal groundwater contribution is indicated by higher electrical conductivity value, warmer temperature, and elevated trace element (i.e., Fe, Li, B, Br, Mn, Al, I and As) concentrations as well as Na and Cl contents in these regions. In the Akarc¸ay basin, chloride and lithium ions, as typical indicators of thermal water contribution, also show a similar distribution to those of temperature and electrical conductivity (Dog˘du and Bayarı 2005). Concentrations of arsenic, antimony and boron are extremely high and are a danger to human health and agricultural production in Balc¸ova geothermal field near ˙Izmir (Aksoy et al. 2009). According to another research, the increases of temperature and electrical conductivity values as well as Na? and Cl- concentrations were determined in irrigation wells which were located in near Hu¨dai geothermal field (Sandıklı-Afyonkarahisar) due to thermal fluid contribution. These contaminated
Environ Earth Sci
groundwaters have been still used as irrigation water in the Sandıklı plain (Aksever 2011). Salinization of groundwater as one of the most important natural pollution types is a major problem in the coastal aquifers of Turkey. Groundwater polluted by seawater intrusion due to excessive abstraction of groundwater from coastal wells. In coastal plains such as C ¸ es¸ me (I˙zmir), Bodrum (Mug˘la), Go¨kc¸eada (C¸anakkale), Marmaris (Mug˘la), C¸anakkale, Erzin (Hatay), Kazanlı (Mersin), Turgutreis (Mug˘la), and Selc¸uk (I˙zmir) groundwater has been either completely or partially affected by seawater (Baba and Deniz 2004; Baba and Yigitbas 2007; Burak et al. 1997; Gemici and Filiz 2001; Gu¨rc¸ay 2004; Demirel 2004; Emekli et al. 1996; Somay and Gemici 2009). Karstification is one of the most important factors affecting seawater penetration into aquifers (Baba and Tayfur 2011). Also, a study carried out in Erdemli (Mersin) between 1999 and 2000 showed that seawater intrusion is also present in this region (Deg˘irmenci and Altın 2001). In a different ¨ zler (2003) studied salinization of groundwater due study, O ¨ zler (2003) concluded to salt intrusion from Lake Van. O that the main processes influencing groundwater chemistry are salt–water intrusion, silicate mineral dissolution, cation exchange, and anthropogenic pollution (Baba and Ayyıldız 2006; Baba and Tayfur 2011). In addition, groundwater nitrate pollution related to human activity and agriculture is a source of rising concern in Turkey. The groundwater in the Eskis¸ ehir plain alluvium has been polluted by municipal and industrial wastewater, and agricultural activities. The nitrate concentrations measured in groundwater from 51 wells ranged between 2.2 and 257.0 mg/l in Eskis¸ ehir urban area (Kac¸arog˘lu and Gu¨nay 1997). Similarly, the groundwater of the Quaternary aquifer in the recharge area of the I˙ncesu-Dokuzpınar spring (Kayseri) has great mineralization, high nitrate pollution, and more depleted heavy-metal contents, especially at the outlet points in the downstream side. The high NO3, NH3, NH4 and PO4 concentrations in the I˙ncesuDokuzpınar springs (Kayseri) reflect the influence of liquid wastes, frequent use of detergents, and widespread farming and stockbreeding around the spring areas (Elhatip et al. 2003). The Sandıklı (Afyonkarahisar) basin is one of the largest agricultural areas in the inner Aegean region. The nitrate contents of groundwater are determined between 0 and 90.12 mg/l in the Sandıklı basin. In the basin, agricultural activities are the most significant anthropogenic sources of nitrate contamination in groundwater (Aksever 2011). Commonly referred to by its Turkish acronym GAP, the Southeastern Anatolia Project includes 22 dams in the upper Euphrates-Tigris Basin, and aims to provide irrigation for 1.7 million hectares of land by 2015 (Unver 1997). The GAP region, and in particular in the Harran Plain, faces problems of salinity, excessive and uncontrolled
irrigation, an insufficient drainage system, and an increased groundwater level caused by irrigation that first started in 1995 (Kendirli et al. 2005). According to research by Yesilnacar and Gulluoglu (2008), the nitrate concentration in groundwater ranges from min. 1.3 mg/l in the north of the Harran plain to max. 806 mg/l in the center of the plain, with an average value of 164 mg/l due to excessive use of artificial fertilizers in intensive agricultural practices. In addition, agricultural contamination was determined in the Torbalı (I˙zmir) region. Nitrite and ammonia concentrations were found to be above drinking water standard (Tayfur et al. 2008). Likewise, nitrate and pesticides contaminations were investigated in groundwater samples of Buca, Konak, Narlıdere, Urla (69 mg/l), Menemen (146.53 mg/l) in I˙zmir (Aslan et al. 2001; Asarog˘lu et al. 1999; Tayfur et al. 2008). According to another research by Nas and Berktay (2006), spatial distributions of nitrate concentrations were evaluated using GIS for the groundwater wells in the city of Konya and surrounding. Although the groundwater was almost safe regarding nitrate pollution by the year 1998, nitrate pollution increased dramatically as the years passed until 2001. In addition, nitrate in groundwater around Manisa region was detected in all wells with max. 127–133 mg/l. The main sources of nitrite and nitrate in groundwater around Manisa region are fertilizers used in agricultural activities (Eryurt and Sekin 2001). Microbiological groundwater contamination caused a serious global environmental and public health problem. The contaminants leading to microbiological pollution are pathogens, and pathogens can produce water-borne diseases in either human or animal hosts. Microbiological groundwater contamination is determined in several region of Turkey. Currently total coliforms, fecal coliforms, Escherichia coli and enterococci are bacterial indicators used in microbiological water quality. The microbiological pollution was assessed using total coliform bacteria, which are collected from springs, wells and distribution system of Tefenni (Burdur) county and villages. In this area, total coliforms were analyzed for 312 water samples which were collected in monthly periods between January 2009 and December 2009. Total coliform counts varied between 0 and 241 for the sampling period (Davraz and Varol 2012). Karagu¨zel and Irlayıcı (1998) revealed that sewage water in the city canals and waste storage are the largest polluters in the Isparta Plain. They concluded that almost two-thirds of the aquifer in the plain was severely polluted from the point of view of microbiological and nitrate contaminations. In another study, Karagu¨zel et al. (1999) showed that groundwater of an aquifer in Antalya, which is an urbanized city, was contaminated by sewage discharge, industrial works, and other activities. Coli bacteria contamination was determined in aquifers of Antalya city.
123
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Therefore, several wells within the city have become unavailable for drinking water (Karagu¨zel et al. 1999). In addition, microbiological contamination was determined at Kırkgo¨zler karstic springs which are located in north of the Antalya. The source of coli bacteria at Kırkgo¨zler spring is Bucak sewage pipe, which is connected into a sinkhole (Karagu¨zel et al. 1995). The C ¸ eltikc¸i Plain, the selected investigation area, is intensively irrigated, and groundwater is the major source for irrigation. In this study, physical, hydrogeological and hydrochemical data from the groundwater system have been integrated and used to determine the major factors and mechanisms controlling the chemistry of groundwater in the C ¸ eltikc¸i plain and to assess its suitability for drinking, domestic, and agricultural uses.
Materials and methods Geological map of the study area is prepared with the help of Corel DRAW X5 software in 1:50,000 scale by utilizing the previous data and information. Groundwater level maps were prepared for the alluvial aquifer with groundwater level data measured in 21 wells during May and October 2012. The hydraulic conductivity and transmissibility coefficients of the alluvial aquifer were determined using well pumping test results of state hydraulic works (SHW) using Aquifer Test 4.0 Pro-software with Cooper-Jacob method. A total 38 water samples were collected periodically in the rainy and dry seasons of 2012. Geographical positions of sampling sites were measured with the help of portable GPS system. Measurements of electrical conductivity (EC), pH and temperature (T) were carried out in situ using a portable multiparameter YSI Professional Plus. Samples were collected in clean polyethylene bottles and dispatched for analysis to the laboratory in an ice-filled box. The major cation and heavy metals were analyzed by ICP-MS (inductively coupled plasma-mass spectrometer) at the ACME Laboratory (Vancouver, Canada) that it has two accreditations (ISO 9001 and ISO/IEC 17025:2005). Spectrophotometer (HCAH DR 2000) was used for determination of nitrate (NO3-), nitrite (NO2-) and ammonium (NH4?) concentrations. Also, cations (Na?, = K?, Ca2?, Mg2?) and anions (Cl-, SO=4 , HCO3 , CO3 ) were measured taking into consideration standards of analyses (TS 4530, TS 4474, TS 3790, TS 4164, EN ISO 9297, TS 5095) in the laboratory of the SHW and Geothermal Energy, Groundwater, Mineral Resources Research Center of Suleyman Demirel University (Isparta, Turkey). An ionic error balance was computed for each chemical sample and used as a basis for checking analytical results. In accordance with international standards,
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results with ionic balance error greater that 5 % were rejected (Appelo and Postma 1993). Charge balances (CB) were calculated using Eq. 1: CB ¼ ½ðRzMc RzMa Þ = ðR zMc þ RzMa Þ
ð1Þ
where z is the ionic charge of cation (c) or anion (a) and M molar concentration of major solutes. Stable isotope analyses were made by International Research and Application Center for Karst Water Resources Stable Isotope Laboratory of Hacettepe University (UKAM). The R-mode factor analysis was carried out using the statistical package for Social Sciences Software (SPSS).
Geology and hydrogeology Geological and hydrogeological properties of the study area were primarily determined. Beydag˘ları Autochthon and allochthonous units belong to Yes¸ ilbarak and Lycian nappes are outcropped in the study area (Fig. 1). Tectonic structure is quite complex in this region due to prevalence of nappes (S¸ enel 1997). Beydag˘ları Autochthon which is located in the Western Taurides is represented by Beydag˘ları formation, C¸amlıdere olistostrome, Ku¨c¸u¨kko¨y, Karakus¸ tepe formations ¨ zdemir 2013). and Tekkeko¨y member in the study area (O Jurassic-Cretaceous aged Beydag˘ları formation consists of grey, white, beige colored, locally dolomitic, neritic limestones (Gu¨nay et al. 1982). Tekkeko¨y member comprises micrites with globotruncana and bedded chert. C ¸ amlıdere olistostrome consists of micrite, claystone, marn, calcarenite, sandstone and clayey micrite (S¸ enel 1997). Ku¨c¸u¨kko¨y formation is composed from claystone, marl, limestone and sandstone rocks (Poisson 1977). Burdigalian aged Karakus¸ tepe formation is composed from intercalated grey, cream, brown colored sandstone, claystone, siltstone (S¸ enel 1997). Elmalı formation belongs to Yes¸ ilbarak nappe. This formation is composed from sandstone and shale with intercalated sandy–clayey limestone, calcarenite and conglomerate. Sandstone levels which are included in the Elmalı formation have iron and manganese ores (S¸ enel 1997). Marmaris ophiolite nappe and Domuzdag˘ nappe which belong to Lycian nappe are situated on the Yes¸ ilbarak nappe. Marmaris ophiolite nappe is characterized with Kızılcadag˘ me´lange and olistostrome and I˙kizpınar fysch member (S¸ enel 1997). In addition, Quaternary alluvium and slope debris and Plio-Quaternary conglomerate are situated in the study area as neo-autochthon cover rocks. The stratigraphic units within the study area have different hydrogeological characteristics. These units are grouped qualitatively as impermeable (aquifuge-Kızılcadag˘ me´lange and olistostrome and I˙kizpınar fysch member), semi-permeable (aquitard-C¸amlıdere olistostrome, Ku¨c¸u¨kko¨y, Karakus¸ tepe and Elmalı formations), permeable-1
Environ Earth Sci
Fig. 1 Geological map of the study area
Fig. 2 Groundwater level map of the study area
(granular aquifer- alluvium and slope debris) and permeable-2 (karstic aquifer- Beydag˘ları formation, Tekkeko¨y ¨ zdemir 2013). Groundmember and Dutdere limestone; O water is taken from alluvium, limestones and sandstone, conglomerate and limestone levels of the Elmalı formation in this area. Alluvium is the most important aquifer in the basin. The groundwater of the study area occurs under
unconfined conditions. The well logs indicate that the thickness of the alluvium ranges from 80 to 160 m in the C¸eltikc¸i plains. Transmissibility coefficient of alluvium aquifer is calculated using Jacob method range between 1.10 9 10-3 and 6.63 9 10-5 m2/s. The permeability coefficient of alluvium aquifer is between 1.02 9 10-5 and ¨ zdemir 2013). 4.40 9 10-7 m/s (O
123
123
372
299
537
463.7
8
8.78
12.63
14.73
0.56
0.6
-0.65
0.42
43.26
50.85
40.32
39.63
TH (mg/ l)b
EC (lS/ cm)a
EC (lS/ cm)b
pHa
pHb
%Naa
%Nab
SARa
SARb
RSCa
RSCb
PIa
PIb
MHa
MHb
6.4
TH (mg/ l)a
b
HCO3
6.79
0.1
a
HCO3
b
SO24
0.18
0.47
2.37
0.24
b
Cl-
b
3
3.61
4.44
0.04
0.04
1.04
1.08
C ¸ eltikc¸i well K-1
a SO24
a
Cl-
Mg2?
Mg
b
2? a
Ca2?
Ca
b
K?
2? a
a
b
Na?
K?
a
Na?
Sample No
Region
8.14
35.98
-1.13
0.11
2.75
8.3
447
362.5
6.12
0.33
0.24
0.59
6.66
0.05
0.21
Dag˘arcık well K-2
8.68
8.48
36.15
29.04
-0.34
-3.05
0.18
0.13
4.19
2.87
8.33
8.07
574
588
432
460
8.3
6.15
0.13
0.3
0.28
0.5
0.75
0.78
7.89
8.42
0.04
0.01
0.38
0.27
Dag˘arcık spring K-3
32.38
33.09
45.75
42.89
-0.61
-1.29
1.01
1.01
19.35
18.57
8.23
8.07
760
792
435.5
486.5
8.1
8.44
1.05
0.93
0.48
0.81
2.82
3.22
5.89
6.51
0.04
0.03
2.1
2.22
Dag˘arcık well K-4
21.63
23.46
32.95
34.11
-3.36
-2.91
0.38
0.44
8.51
9.3
8.35
8.09
700
717
423
454
5.1
6.17
0.33
0.1
1.9
2.31
1.83
2.13
6.63
6.95
0.03
0.03
0.79
0.93
Seydiko¨y well K-5
7.94
9.21
44.53
39.84
-0.04
-0.76
0.13
0.15
3.81
3.94
8.53
8.3
394.1
411.8
277
315
5.5
5.54
0.2
0.06
0.2
0.45
0.44
0.58
5.1
5.72
0.02
0.02
0.22
0.26
C¸eltikc¸i well K-6
41.08
44.18
39.83
33.98
-0.73
-1.92
0.43
0.35
9.56
7.33
8.6
8.32
567
623
406.5
485.5
7.4
7.79
0.55
0.48
0.3
0.77
3.34
4.29
4.79
5.42
0.01
0.01
0.86
0.77
C¸ebis¸ well K-7
25.85
27.22
39.74
37.99
-0.90
-1.02
0.2
0.2
5.24
4.98
8.52
8.35
479.2
481.2
325
354.5
5.6
6.07
0.38
0.07
0.26
0.44
1.68
1.93
4.82
5.16
0.01
0.02
0.36
0.37
C¸ebis¸ well K-8
Table 1 Hydrogeochemical characteristics of groundwater in the C¸eltikc¸i plain
26.95
31.50
-2.49
0.19
4.38
8.37
555
449
6.49
0.62
0.35
2.42
6.56
0.03
0.41
Bag˘saray well K-9
28.50
41.29
-0.91
0.23
6.1
8.41
384.3
303.5
5.16
0.51
0.33
1.73
4.34
0.03
0.4
Bag˘saray well K-10
8.63
9.25
46.83
43.49
-0.15
-0.52
0.1
0.1
3.05
3.08
8.78
8.56
313.5
308.4
237.5
259.5
4.6
4.67
0.11
0.09
0.1
0.2
0.41
0.48
4.34
4.71
0.01
0.02
0.15
0.17
Akyayla spring K-11
11.14
12.15
47.58
43.18
-0.19
-0.66
0.08
0.09
2.6
2.79
8.8
8.55
302.8
305.1
224.5
251
4.3
4.36
0.11
0.04
0.08
0.24
0.5
0.61
3.99
4.41
0.01
0.01
0.12
0.14
Kayıs¸ spring K-12
16.85
17.71
44.39
41.25
-0.40
-0.75
0.18
0.17
5.09
4.66
8.81
8.43
367.6
374.6
270
296.5
5
5.18
0.22
0.16
0.13
0.31
0.91
1.05
4.49
4.88
0.01
0.01
0.29
0.29
Ovacık well K-13
36.23
34.53
-1.36
0.47
8.98
8.37
748
559
9.82
0.25
0.97
4.05
7.13
0.05
1.11
Kuzko¨y well K-14
30.20
31.64
43.49
39.25
-0.49
-1.04
0.37
0.37
9.21
8.51
8.79
8.39
481.4
516
324.5
384
6
6.64
0.55
0.15
0.29
0.8
1.96
2.43
4.53
5.25
0.02
0.02
0.66
0.72
Kuzko¨y well K-15
33.07
36.07
-1.66
0.26
6.17
8.58
626
387
6.08
0.73
0.67
2.56
5.18
0.01
0.51
Gu¨venli spring K-16
24.77
37.84
-0.65
0.19
4.65
8.55
520
377.5
6.9
0.41
0.2
1.87
5.68
0.03
0.37
Bag˘saray well A-1
35.69
35.73
-1.67
0.35
7.66
8.65
685.3
438.5
7.1
0.67
0.49
3.13
5.64
0.03
0.73
Bag˘saray well A-2
33.33
34.84
-0.70
0.35
7.15
8.73
704
525
9.8
0.76
0.4
3.5
7.0
0.02
0.81
Kuzko¨y well A-3
Environ Earth Sci
Ca–Mg– HCO3 Ca–Mg– HCO3
Results and discussion
Ca– Mg– HCO3
Ca– Mg– HCO3 Ca– Mg– HCO3
Ca– HCO3 Ca– HCO3 Ca– HCO3
Ca– HCO3 Ca– HCO3 Ca– HCO3 Ca– HCO3
October 2012, anions and cations in meq/l
July 2012 a
Ca– Mg– HCO3 Water Classb
b
Ca– HCO3
Ca–Mg– HCO3
Ca– HCO3
Ca– HCO3
Ca– Mg– HCO3
Ca– HCO3
Ca– HCO3 Ca– HCO3 Ca– Mg– HCO3 Ca– HCO3 Ca– HCO3 Ca–Mg– HCO3 Ca– HCO3 Ca– HCO3 Ca– Mg– HCO3 Water Classa
Sample No
Groundwater geochemistry
Ca– Mg– HCO3
Gu¨venli spring K-16 Dag˘arcık well K-2 C ¸ eltikc¸i well K-1 Region
Table 1 continued
Dag˘arcık spring K-3
Dag˘arcık well K-4
Seydiko¨y well K-5
C¸eltikc¸i well K-6
C¸ebis¸ well K-7
C¸ebis¸ well K-8
Bag˘saray well K-9
Bag˘saray well K-10
Akyayla spring K-11
Kayıs¸ spring K-12
Ovacık well K-13
Kuzko¨y well K-14
Kuzko¨y well K-15
Kuzko¨y well A-3
Ca– Mg– HCO3
Bag˘saray well A-2
The seasonal variation in groundwater level is associated with rainfall and groundwater abstraction for irrigation. The groundwater depth varies from 0.49 to 11.78 m in the C¸eltikc¸i plain and groundwater level map was prepared ¨ zdemir 2013). in May 2012 (Fig. 2; O
Bag˘saray well A-1
Environ Earth Sci
Weathering, ion-exchange processes and inputs from the atmospheric and anthropogenic sources are the major solute acquisition mechanism controlling the concentration of chemical constituents in the groundwater. The relative proportion of various dissolved ions in water depends on their abundance in the host rocks/aquifer and their solubilities (Sarin et al. 1989; Singh and Hasnain 1999). The hydrogeochemical data can be used to gain insight into the possible source of dissolved ions in water. Electrical conductivity (EC) of water is directly related to the concentration of dissolved solids in the water, and is important parameter for usability classifications of waters. The EC values of groundwater vary within a range 305.1–792 lS/cm in dry season and 302.8–760 lS/cm in wet season (Table 1). The pH of groundwater varies from 8.0 to 8.58 in dry and 8.23 to 8.81 during wet seasons, indicating alkaline nature of groundwater. A slight increase in pH was noticed in the wet season in comparison to dry season. The availability of dissolved ions in groundwater system is influenced by the different geochemical processes that operate in the subsurface hydrogeologic system. Therefore, the availability of these ions present in aquifers becomes a useful tool in the identification of geochemical processes (Nur et al. 2012). The relative abundance of cations in groundwater within the study area is in the order: Ca2? [ Mg2? [ Na? [ K, and anions is in the order: HCO3- [ SO42- [ Cl- and HCO3- [ Cl- [ SO42(Fig. 3). Cation concentrations and ionic ratios can trace water–rock interaction processes, such as mineral weathering and cation exchange (Han et al. 2009). Calcium and magnesium concentrations in groundwater vary from 3.61 to 8.42 meq/l and from 0.41 to 4.29 meq/l, respectively (Table 1). Ca2? can be derived from dissolution of carbonate minerals (e.g., calcite, dolomite, aragonite) as well as carbonate cement within formations. The primary source of Mg2? in natural water is ferromagnesian minerals (olivine, diopside, biotite, hornblend) within igneous and metamorphic rocks and magnesium carbonate (dolomite) in sedimentary rock (Singh et al. 2012). The major source of Mg2? in groundwater is probably Mg-bearing minerals such as dolomite and magnesium sulfate minerals in the study area.
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Environ Earth Sci
Fig. 3 Hydrogeochemical map of the study area (June 2012)
Calcium and magnesium are the dominant ions of groundwater, suggesting dissolution of carbonate minerals in the area. During infiltration, groundwater may dissolve the CaCO3 and CaMg(CO3)2 present in the rocks, and increase the calcium and magnesium ions in groundwater. In the study area, weathering is one of the key geochemical processes which controlled the solute concentration in groundwater. The (Ca ? Mg) vs. (HCO3 ? SO4) scatter diagram shows that most of the samples are falling above the equiline of 1:1 in the wet season, thus indicating carbonate weathering as a major source of Ca and Mg (Datta and Tyagi 1996; Fig. 4a). In the dry season, majority of the samples fall along the equiline 1:1, suggesting that these ions have resulted from weathering of carbonates and silicates (Datta et al. 1996; Rajmohan and Elango 2004; Kumar et al. 2006). The ionic concentrations falling above the equiline result from carbonate weathering, while those falling along the equiline are due to both carbonate weathering (Eqs. 2–4) and silicate weathering (Eqs. 5, 6; Dehnavi et al. 2011). The HCO3 derives mainly from the soil zone CO2 at the time of weathering of minerals of the parent rocks. The soil zone in the subsurface environment contains elevated CO2 pressure due to the decay of organic matter and root respiration, which, in turn, combines with rainwater (H2O) to form HCO3 (Eqs. 2–4; Rao and Rao
123
2010; Kumar et al. 2009). The significant reduction of Na concentration may be due to ion-exchange process (Fig. 4b). The high concentration of bicarbonate among the anions could be attributed to silicate weathering. Silicate weathering increases the concentration of HCO3 in groundwater (Dehnavi et al. 2011). CO2 þ H2 O ) H2 CO3 ðFormation of carbonic acidÞ ð2Þ CaCO3 ðcalciteÞ þ H2 CO3 ðcarbonic acidÞ ) Ca2þ þ 2HCO 3 ðCalcite dissolutionÞ
ð3Þ
CaMgðCO3 Þ2 ðdolomiteÞ þ 2H2 CO3 ðcarbonic acidÞ ) Ca2þ þ Mg2þ þ 4HCO 3 ðDolomite dissolutionÞ ð4Þ NaAlSi3 O8 ðAlbiteÞ þ H2 CO3 þ 4:5H2 O ) Naþ þ HCO 3 þ 2H4 SiO4 ðKaoliniteÞ þ 0:5Al2 Si2 O5 ðOHÞ4
ð5Þ
CaAl2 Si2 O8 ðAnorthiteÞ þ 2H2 CO3 þ H2 O ) Ca2þ þ 2HCO 3 ðKaoliniteÞ þ Al2 Si2 O5 ðOHÞ4 ð6Þ A Ca2?/Mg2? ratio of 1 shows the dissolution of dolomite, whereas a higher ratio is indicative of greater calcite
Environ Earth Sci
Fig. 4 Graphs of different parameters
contribution (Maya and Loucks 1995). Ca2?/Mg2? ratio[2 indicates the dissolution of silicate minerals which could contribute calcium and magnesium to groundwater (Katz et al. 1998). The Ca/Mg ratios in the groundwater samples of the study area (79 %) having a ratio [2 indicate the effects of silicate minerals (Fig. 4c). In addition, all of groundwater within the study area had Mg2?/ (Ca2? ? Mg2?) equivalent ratios \0.5, suggesting limestone and dolomite or dolomite weathering, and these weathering processes are responsible for the sources of Mg2? and Ca2? in groundwater within the area. Further, 100 % of groundwater had Ca2?/(Ca2? ? SO=4 ) equivalent ratios [0.5, suggesting calcium source other than gypsum– carbonates, calcite/dolomite or silicates. Thus, calcite/
dolomite carbonates or silicate dissolution may have contributed significantly to the concentrations of Ca2? and Mg2? (Tay 2012). In addition, the ratio of HCO3-/SiO2 in a water sample can also reveal the type of weathering process taking place in an aquifer. A ratio of HCO3-/ SiO2 \ 5 indicates silicate weathering process, while that of HCO3-/SiO2 [ 10 indicates carbonate weathering process (Tay 2012). This study showed that all of groundwater had HCO3-/SiO2 ratios [10, confirming carbonate weathering as the major weathering process taking place in aquifers in the C¸eltikc¸i plain. Ion exchange process is also another key geochemical process controlling the solute concentration in groundwater. Because of their electrical charge, the ions in water
123
Environ Earth Sci
have a tendency to be attracted onto solid surfaces. Such surfaces include ordinary mineral grains (e.g., feldspar or quartz) but these are much less efficient than the surfaces of minerals such as iron oxides and clay minerals. Both anions and cations take part in ion-exchange processes. Clays are particularly effective at adsorbing cations because their surfaces are consistently negatively charged. The ions of different elements have different tendencies to be adsorbed or desorbed. The tendency for adsorption amongst the major cations in natural waters is as follows: ðstrongly adsorbedÞ Ca2þ [ Mg2þ [ Kþ [ Naþ ðweakly adsorbedÞ which means that calcium ions are much more likely to be adsorbed onto surfaces than are sodium ions (Deutsch 1997). Na vs. Ca scatter diagram shows increased concentration of Ca2? compared to Na? that indicates ion exchange (Nur et al. 2012; Dehnavi et al. 2011; Fig. 4d). It shows that the ion-exchange process appears as responsible for contributing higher concentration of Ca2? in the groundwater (Dehnavi et al. 2011; Elango et al. 2003). Sodium concentrations in groundwater vary from 0.12 to 1.04 meq/l and from 0.14 to 2.22 meq/l in dry and wet seasons, respectively. Na concentration increased in three locations (K1-1.08 meq/l, K4-2.22 meq/l, K14-1.11 meq/l; Table 1). Wells in these locations are drilled within the Elmalı formation which is composed of sandstone, shale, sandy– clayey limestone, calcarenite and conglomerate levels. These units contain sodium minerals such as Albite (NaAlSi3O8) and clays minerals. If halite dissolution is responsible for sodium, the Na/Cl ratio should be approximately equal to 1, whereas a ratio [1 is typically interpreted as Na released from silicate weathering reactions (Meyback 1987; Kumar et al. 2006; Tay 2012). In the present study, the Na/Cl ratio of groundwater samples generally varies from 1.1 to 5.7 in dry season (Fig. 4e). Samples having Na/Cl ratio greater and less than 1 in the study area are nearly equal and hence sodium might have come from irrigation return flow, anthropogenic activity and silicate weathering. (Pazand et al. 2012; Pazand and Hezarkhani 2013; Bhat et al. 2013). The evidence for ion exchange in the development of salinization can lead to release of Na? from clay products within the Elmalı formation, replacing Ca2? that is present in groundwater (Gibrilla et al. 2010). Clays are particularly effective at adsorbing cations because their surfaces are consistently negatively charged (Mcbride 1997). Some sodium may be derived from Na-bearing silicate minerals, such as albite (Pazand and Hezarkhani 2013). Ion exchange is a type of adsorption/desorption phenomenon. Clay minerals are the most common ion
123
exchangers in soil and aquifer system. Cations present in the clay and groundwater are easily exchangeable than anion. pH of a solution also controls the exchange processes (Elango and Kannan 2007). If huge amount of Na content is reduced from groundwater, it is attributed to ionexchange process (Dehnavi et al. 2011). The chloroalkaline index (CAI) (Schoeller 1965, 1967) indicates the ion exchange between the groundwater and its host environment. CAI calculated using Eqs. 7 and 8 was further used to verify the existence of ion-exchange reactions in the study area. If there is ion exchange of Na? and K- from water with magnesium and calcium in the rock, the exchange is known as direct when the indices are positive. If the exchange is reverse then the exchange is indirect and the indices are found to be negative. The negative CAI values in study area suggest that magnesium and calcium from water are exchanged with sodium and potassium in rock favoring cation–anion exchange reactions (Schoeller 1967; Kumar et al. 2007; Jankowski et al. 1998; Fig. 4f). CAI 1 ¼ ½ClðNa þ KÞ= Cl
ð7Þ
CAI 2 ¼ ½ClðNa þ KÞ=ðSO4 þ HCO3 þ NO3 Þ
ð8Þ
(all values expressed in meq/l). Consistent with the chemistry of most natural waters, HCO3- is the dominant anion, while SO=4 and Cl- occur in minor concentrations (Freeze and Cherry 1979). Chebotarev (1955) has shown that bearing local variations, which may result from an abnormal concentration of certain constituents in the soil, the composition of groundwater varies from bicarbonate (HCO3-) at outcrops to sulfate (SO42-) water at intermediate depths to chloride (Cl-) waters at greater depths of continuous flow (Tay 2012). Bicarbonate (HCO3-) concentrations were determined as a range 5.0–9.80 meq/l in dry season and 4.36–9.82 meq/l in wet season (Table 1). The bicarbonate concentration in groundwater is derived from carbonate weathering as well as dissolution of carbonic acid in the aquifers. The concentration of chloride varied as a range 0.08–2.31 meq/l. The increase of chloride concentration is measured in K5 location it may be associated with anthropogenic and geogenic activities. But, this well is cut Elmalı formation and Kızılcadag˘ me´lange, and it is situated in the marble plant. Sulfate occurs naturally in water as a result of leaching from gypsum and other common minerals (Alam et al. 2012). Sulfate concentrations of groundwater were determined as 0.1–1.05 meq/l in dry season and 0.06–0.93 meq/ l in wet season (Table 1). The source of SO42- in the water samples is gypsum and other minerals within the Elmalı formation in the study area. Major cations and anions such as Ca2?, Mg2?, Na?, K?, HCO3-, SO42- and Cl- (in meq/l) were plotted in piper trilinear diagram (Piper 1944) to evaluate the
Environ Earth Sci Fig. 5 Piper trilinear diagram showing chemical characters of groundwater and hydrogeochemical facies
hydrochemistry of groundwater of C¸eltikc¸i plain (Fig. 5). The dominant water types are Ca–HCO3 and Ca–Mg– HCO3. The plot shows that most of the groundwater samples fall in the field of alkaline earth metals (Ca2?, Mg2?) dominating over the alkalies (Na?, K?) and weak acid (CO32-, HCO3-) exceed the strong acid (Cl-, SO42-).
Total hardness (TH, as CaCO3) is an important property for water quality assessment. The classification of groundwater based on total hardness (Sawyer and McCartly 1967) shows that all of the groundwater samples fall in the very hard water category (Tables 1, 2). Total hardness (TH) was calculated by the following equation (Ragunath 1987), where TH is expressed in mg/l.
Drinking and irrigation water quality
TH ¼ ðCa þ MgÞ 50
Quality of groundwater determines its suitability for different purposes depending upon the specific standards. To assess the suitability for drinking, the hydrogeochemical parameters of the groundwater of the study area are compared with the prescribed limits of WHO (2006) and Turkish Drinking Water Standards (TSE 266, 2005). Major ? 2? anions (HCO3-, CO32-, Cl-, SO24 ), cations (Na , Ca , Mg2?, K?) analyses and physical parameters (EC, pH, temperature) in the analyzed groundwater samples, are found within the recommended limits and can be used for drinking purposes.
Maximum allowable limit of TH for drinking is 500 mg/l and the most desirable limit is 100 mg/l as per the WHO international standard. TH values of groundwater in the study area ranges between 224.5 and 559 mg/l and in *7 % some samples exceed the maximum allowable limits. In addition, Schoeller drinkable diagram is used for evaluating of usability as drinking water of groundwater in the study area. According to Schoeller’s diagram, the groundwater was classified as ‘very good quality drinkable water’ for both periods (Fig. 6). On the other hand,
ð9Þ
123
Environ Earth Sci Table 2 Classification scheme for drinking and irrigation water quality Classification scheme
Categories
Ranges
TH (Sawyer and McCarthy 1967)
Soft
\75
Moderately hard
75–150
Hard
150–300
EC (Wilcox 1955)
SAR (Richards 1954)
Na % (Wilcox 1955)
RSC (Richards 1954)
PI (Doneen 1964; WHO 1989)
MH (Szabolcs and Darab 1964)
Very hard
[300
Excellent
\250
Good
250–750
Permissible Doubtful
750–2,250 2,250–5,000
Unsuitable
[5,000
Excellent
\10
Good
10–18
Doubtful
18–26
Unsuitable
[26
Excellent
0–20
Good
20–40
Permissible
40–60
Doubtful
60–80
Unsuitable
[80
Good
\1.25
Medium
1.25–2.5
Bad
[2.5
Class I Class II
[75 % 25–75 %
Class III
\75 %
Unsuitable for irrigation
[50 %
Suitable for irrigation \50 %
groundwaters in the study area fall in ‘good quality drinkable water’ class according to this diagram due to high electrical conductivity (EC) and total hardness (TH) values. Groundwater is the main source for domestic and agricultural activities. Most of the study area is covered by agricultural lands and residents. The suitability of groundwater for irrigation purposes depends upon the effect of mineral constituents of water on both plants and soils (Srinivasa Gowd 2005; Raju 2007). Different hydrochemical parameters such as sodium absorption ratio (SAR), sodium percentage (%Na), residual sodium carbonate (RSC), permeability index (PI) and Magnesium hazard (MH) are used to assess the suitability of groundwater for agricultural purposes. Sodium absorption ratio (SAR) SAR is a measure of the suitability of water for use in agricultural irrigation, as determined by the concentrations
123
of solids dissolved in the water. It is also a measure of the sodicity of soil, as determined from analysis of water extracted from the soil. It is calculated by the following formula (where the concentrations of all ions are in meq/l): rNaþ ffi: SAR ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi þþ ðrCa þ rMgþþ Þ=2
ð10Þ
The SAR value was calculated as a range 0.09–1.01 and it can be classified as excellent category for irrigation uses (Tables 1, 2). The plot of data on the US salinity diagram (Fig. 7), in which the EC is taken as salinity hazard and SAR as alkalinity hazard, shows that majority of the water samples fall in the category C2S1, indicating medium salinity and low alkali water. Such water can be used for irrigation in most soil and crops with little danger of development of exchangeable sodium and salinity. However, two groundwater samples (K4, K5) fall in the zone of C3S1 indicating high salinity and low alkali water. The increase of EC value in these groundwater samples is originated from anthropogenic impacts. Sodium percentage (%Na) Sodium concentration is important in classifying irrigation water because sodium reacts with soil to reduce its permeability. Sodium content is usually expressed in terms of percent sodium (also known as sodium percentage and soluble-sodium percentage), defined by: %Na ¼
rNaþ 100 rNa þ rCa þ rMgþþ þ rKþ þ
þþ
ð11Þ
where all ionic concentrations are expressed in meq/l. The sodium percent (%Na) is calculated between 2.75 and 18.57 and 2.60 and 19.35 in July 2012 and October 2012, respectively. It is observed that all of groundwater samples fall within the category of excellent (Table 1). In addition, plot of analytical data on Wilcox diagram (Wilcox 1955) relating EC and %Na shows that water samples are of excellent to good and good to permissible quality for irrigation (Fig. 8). Residual sodium carbonate (RSC) Residual sodium carbonate (RSC) has been calculated to determine the hazardous effect of CO=3 and HCO3- on the quality of water for agricultural purpose (Eaton 1950). The RSC value was calculated, using the relation: 2þ ð12Þ RSC ¼ CO¼ þ Mg2þ 3 þ HCO3 Ca where ionic concentrations are expressed in meq/l. The RSC in groundwater varied from -3.36 to 0.42 meq/l (Table 1). Negative RSC indicates that Na?
Environ Earth Sci Fig. 6 Schoeller drinkable diagram
buildup is unlikely since sufficient Ca2? and Mg2? are in excess of what can be precipitated as CO=3 (Ramesh and Elango 2012)..All groundwater samples in the study area are within the good categories for irrigation according to RSC values (Table 2). Permeability index (PI) The soil permeability is affected by the long-term use of irrigation water as it is influenced by Na?, Ca2?, Mg2? and HCO3- content of the soil (Ramesh and Elango 2012). WHO (1989) gave a criterion for assessing the suitability of groundwater for irrigation based on the PI, where concentrations are in meq/l (Ragunath 1987; Aghazadeh and Mogaddam 2011). It is defined as:
PI ¼ 100 ½ðNaþ þ
p
þ 2þ HCO þ Mg2þ Þ: 3 Þ=ðNa þ Ca
ð13Þ According to PI values, the groundwaters of in the study area are ranged from 31.50 to 50.85 % (Table 1) and represented class II (25–75 %) indicating that the groundwater is unsuitable for irrigation. Magnesium hazard (MH) The excess of Mg affects the quality of soil resulting in poor agricultural returns. The magnesium hazard (MH) is proposed by Szabolcs and Darab (1964) for irrigation water as following formula. MH ¼ 100 Mg2þ = Mg2þ þ Ca2þ ð14Þ
123
Environ Earth Sci Fig. 7 US salinity diagram for classification of irrigation water
MH [50 is considered harmful and unsuitable for irrigation use. The MH value in the groundwater of study area varies between 8.14 and 44.18 % (Table 1). In the analyzed groundwater samples, MH is \50. The MH indicates that the groundwater is not harmful for irrigation. Groundwater contamination The porous soils of the study area are characterized by high infiltration and low moisture retention. Groundwater is the main source for domestic and agricultural usage. Most of the study area is covered by agricultural lands and residents. Hence, groundwater contamination by irrigation return flow, fertilizer and farm manure application, leaching of soil mineralized nitrogen, domestic sewage, runoff and leached rainfall water, etc., is also an important issue on groundwater contamination in the study area. To determine contamination problem in the study area,
123
nitrogen compounds (NO3-, NO2-, NH4?) and trace elements (Fe, Mn, Cu, Zn, Pb, As, Cr) were analyzed in the groundwater samples (Table 3). Nitrate (NO3-) Nitrogen (N) is an essential input for the sustainability of agriculture (Almasri 2007; Delgado 2002; Lake et al. 2003). Nitrate and nitrite are soluble compounds containing nitrogen and oxygen. In the environment, nitrite (NO2-) generally converts to nitrate (NO3-), which means nitrite occurs very rarely in groundwater. Nitrate is soluble and negatively charged and thus has a high mobility and potential for loss from the unsaturated zone by leaching (DeSimone and Howes 1998; Chowdary et al. 2005). Many studies showed high correlation and association between agriculture and nitrate concentration in groundwater (Harter et al. 2002; Dunn et al. 2005; Liu et al. 2005). The
Environ Earth Sci Fig. 8 Wilcox diagram for classification of groundwater based on EC and %Na
natural nitrate concentration in groundwater under aerobic conditions is a few milligrams per litre and depends strongly on soil type and on the geological situation. But, nitrate concentrations grow due to human activities, such as agriculture, industry and domestic waste. The maximum contaminant level of nitrate is given to be 50 mg/l in Turkish Standards Institute (TSE-266 2005) and World Health Organization (WHO 2008). However, if nitrate concentration is over 10 mg/l, it is indicated that groundwater is affected by anthropogenic factors. US Environmental Protection Agency (EPA 2012)’s maximum contaminant level for nitrate set to protect against bluebaby syndrome is 10 mg/l. Seasonal variations were observed in nitrate concentrations of groundwater from wells and springs in the study area. Nitrate concentration of groundwater varies from 0.23 to 26.15 mg/l in wet and 1.81 to 106.24 mg/l during dry
season, respectively (Table 3). In general, low concentrations were measured in the wet seasons and high concentrations during the dry seasons. The increase of nitrate concentrations in groundwater demonstrated the effects of agricultural activities. About 20 % of the samples in dry season exceeded the recommended maximum allowable value for nitrate in potable water according to the WHO (50 mg/l NO3-), which indicated that the groundwater had not been severely polluted by nitrate in this aquifer system. Trace elements in subsurface environments come from geogenic and anthropogenic sources. The weathering of minerals is one of the major natural sources. Ion exchange is also an important process for trace elements. Clay– mineral bearing rocks and sediments will naturally adsorb heavy-metal cations from contaminated water (Deutsch 1997). Anthropogenic sources include fertilizers, industrial effluent and leakage from service pipes. In the study area,
123
123
b
October 2012
July 2012
11.29
a
d-excess
7.94
NO3 (mg/l)a
2.59
\0.01
NO2 (mg/l)b
-43.03
0.019
NO2 (mg/l)a
d3H
\0.06
NH4 (mg/l)b
d2H
0.002
NH4 (mg/l)a
18.35
14.2
Cr (lg/l)b
-6.79
19.2
Cr (lg/l)a
NO3 (mg/l)b
10
Fe (lg/l)b
d18O
1.1
3
As (lg/l)a
33
0.2
Pb (lg/l)b
Fe (lg/l)a
0.4
Pb (lg/l)a
As (lg/l)b
20.7
Zn (lg/l)b
Cu (lg/l)a
0.6
0.7
Mn (lg/l)b
38.7
1.42
Mn (lg/l)a
Zn (lg/l)a
1.71
Sample no
Cu (lg/l)b
C¸eltikc¸i well K-1
Region
12.83
-48.37
-7.65
3.54
0.028
0
2.2
62
3
0.2
3
1.4
0.81
Dag˘arcık well K-2
13.38
-48.22
-7.70
9.08
0.23
\0.01
0.031
\0.06
0
1.8
2.6
99
122
\0.5
4.4
1.6
0.3
580
3.3
4.2
0.9
3.44
1.3
Dag˘arcık spring K-3
10.71
-43.37
-6.76
42.78
17.06
\0.01
0.03
\0.06
0
5.9
5.9
288
287
0.9
4.7
1.1
0.5
737.3
20.2
4.1
2.6
378.5
241.8
Dag˘arcık well K-4
9.2
-43.52
-6.59
106.24
26.15
\0.01
0.037
\0.06
0.016
5
4.8
16
115
1
5.4
\0.1
0.4
1.9
8.9
0.8
1.2
0.4
1.44
Seydiko¨y well K-5
13.36
3.34
-52.32
-8.21
15.39
4.21
\0.01
0.009
\0.06
0
2
1.3
68
99
\0.5
5.2
0.3
0.4
10.4
4.3
3.3
1.5
0.31
0.94
C¸eltikc¸i well K-6
14.23
-49.13
-7.92
15.57
8.04
\0.01
0.02
\0.06
0
9.9
13.8
262
143
1.6
5.5
0.4
0.2
14.8
6.8
1.3
1.2
23.96
9.74
C¸ebis¸ well K-7
16.16
-52.00
-8.52
44.75
13.94
\0.01
0.004
\0.06
0.008
16.1
13.8
226
206
\0.5
4.9
0.3
4.2
32.7
98.4
1.3
4.6
11.69
11.48
C¸ebis¸ well K-8
15.58
-55.46
-8.88
8
0.005
0
5.4
87
4.8
0.3
22.1
1.1
1.54
Bag˘saray well K-9
Table 3 Trace element and stable isotope contents of the groundwater in the study area
12.93
-56.03
-8.62
4.49
0.02
0.017
3.9
172
5.6
0.6
11.2
1.5
1.39
Bag˘saray well K-10
18.02
4.53
-54.70
-9.09
1.81
0.63
\0.01
0.012
\0.06
0
1.4
1.4
40
147
\0.5
4.7
0.1
0.9
271.7
118.1
0.7
1.6
0.65
3.49
Akyayla spring K-11
14.93
-59.07
-9.25
16.98
4.36
\0.01
0.024
\0.06
0
2
2.6
46
179
\0.5
5.3
0.1
1.6
4.9
48.9
0.6
2.4
1.02
3.09
Kayıs¸ spring K-12
15.71
-53.01
-8.59
26.87
7.14
\0.01
0.007
\0.06
0.032
3.5
3.5
60
193
\0.5
6.6
0.4
0.3
15.4
6
1.3
2.3
0.49
1.58
Ovacık well K-13
4.31
0.032
0.003
3.3
149
7.3
0.3
8.1
3.1
3.87
Kuzko¨y well K-14
14.12
4.50
-49.72
-7.98
12.07
5.38
\0.01
0.012
\0.06
0.033
7.9
6.8
47
152
\0.5
5.7
0.5
0.4
5.5
47.8
0.9
1
2.45
2.67
Kuzko¨y well K-15
15.92
-49.44
-8.17
4.78
0.017
0.02
0.9
227
5.5
0.3
3.4
1.3
1.28
Gu¨venli spring K-16
23.8
\0.01
\0.06
5.8
20
\0.5
\0.1
204.6
0.7
0.45
Bag˘saray well A-1
77.61
\0.01
\0.06
14
32
\0.5
\0.1
7.1
0.9
0.8
Bag˘saray well A-2
3.15
\0.01
\0.06
9.4
362
\0.5
0.8
74.1
2.4
82.09
Kuzko¨y well A-3
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Environ Earth Sci
Cu, Fe, Mn, Cr, Pb and Zn are commonly determined as trace elements in groundwater. Manganese (Mn) Many igneous and metamorphic minerals contain divalent manganese as a minor constituent. It is a significant constituent of basalt and many olivines and of pyroxene and amphibole. Small amounts commonly are present in dolomite and limestone, substituting for calcium. In aquifer, groundwater comes in contact with these solid materials dissolving them, releasing their constituents, including Mn to the water. Groundwaters may contain more than 1 mg/l of manganese under some circumstances. High iron concentrations may accompany the manganese, but this is not invariably true (Hem 1985). As components of groundwater, Fe and Mn are rarely anthropogenic, but rather are introduced to groundwater through natural interactions of water with rock (Daughney 2003). In this study, the Mn contents in the groundwater samples were determined between 0.81 and 241.8 lg/l in wet season. In dry season it is changed from 0.31 to 378.5 lg/l (Table 3). The permissible limit value of Mn for drinking water is 400 lg/l according to WHO (2008) standards, but according to Turkish drinking water standards (TSE-266 2005) and US Environmental Protection Agency (EPA 2012) permissible limit for Mn is 50 lg/l for drinking and domestic water, and is 20 lg/l for natural spring waters. The extreme value of Mn is determined in K4 sample. This well is situated within a ranch in the Dagarcık village. But, animal manure in the ranch contains Mn as well as nitrogene, phosphate (P2O5), Ca, Cu, Mg (Seefeldt 2013). This increase of Mn concentration is originated from anthropogenic effects. In addition, the Mn concentration is analyzed as 82.09 lg/l in the A3 well. The Elmalı formation is cut in this well which is drilled within alluvium aquifer. Sandstone levels which are included in the Elmalı formation have iron and manganese ores (S¸ enel 1997). So, the increase of Mn content is originated from geogenic sources with water–rock interaction. Iron (Fe) Iron is the most commonly available metal on planet earth. Igneous rock minerals whose iron content is relatively high include the pyroxenes, the amphiboles, biotite, magnetite, and especially, the nesosilicate olivine. The main naturally occurring iron minerals are magnetite, hematite, goethite and siderite. Weathering processes release the element into waters. Both mineral water and drinking water contain iron carbonate. Iron in these minerals is in the ferrous, Fe2?, oxidation state, but ferric (Fe3?) may also be present, as in magnetite, Fe3O4. When these minerals are attacked by
water, the iron that may be released is generally re-precipitated nearby as sedimentary species (Hem 1985). Usually there is a difference between water-soluble Fe2? compounds and generally water insoluble Fe3? compounds. The latter are only water soluble in strongly acidic solutions, but water solubility increases when these are reduced to Fe2? under certain conditions (http://www. lenntech.com/periodic/water/iron/iron-and-water). Most groundwater has at least trace amounts of iron because its presence in nature is so common (Taft et al. 1997). The iron concentration of water samples within the study area is changed between 10 and 362 and 33 and 287 lg/l in dry season and wet season, respectively (Table 3). The permissible limit of Fe for drinking water is 300 lg/l according to EPA (2012) standards, but according to Turkish drinking water standards (TSE-266 2005), the permissible limit for Fe is 200 lg/l. Iron concentrations exceeding this level may cause the characteristic reddish staining. Generally, Fe concentration of groundwater is increased in the wet season. This increase is clearly observed at K3, K5, K11, K12, K13 and K15 locations. The increase of Fe is responsible for sandstone levels of the Elmalı formation due to water–rock interaction likewise Mn. Copper (Cu) Copper forms rather stable sulfide minerals; some of the common species that are important as ore minerals also contain iron (Hem 1985). Copper founded in the Earth’s crust rocks as sulfide minerals (chalcopyrite, chalcocite) including natural copper or copper sulfide and carbonate minerals (malachite, azurite) (Goldschimidt 1958). A very small part of the copper in natural waters is natural origin because copper minerals have low solubility (Hem 1985). Copper usually found at trace amount (until 0.05 mg/l) in natural water (McNeely et al. 1979). In this study, the copper (Cu) contents in the groundwater samples were determined between 0.6 and 4.2 and 0.7 and 4.6 lg/l in dry and wet season, respectively (Table 3). The permissible limit of Cu for drinking water is 2,000 lg/l according to WHO (2008) and is 1,000 lg/l according to EPA (2012) standards. Generally, the increase of Cu contents of groundwater is related to agricultural activity. Usually water-soluble copper compounds occur in the environment after release through application in agriculture (http://www.lenntech.com/peri odic/elements/cu.htm). Zinc (Zn) Zinc has about the same abundance in crustal rocks as copper or nickel and is thus fairly common. However, zinc
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has only one significant oxidation state, Zn2?, and tends to be substantially more soluble in most types of natural water than are the other two metals (Hem 1985). In several countries, there is great concern about the excessive inputs of heavy metals, specifically Cu and Zn in agriculture (Haygarth and Jarvis 2002). Copper and zinc are also used as insecticides or fungicides. All these metals are present in industrial wastes and sewage sludges (http://www.pca. state.mn.us/water/groundwater). Zinc contents of groundwater were changed 1.9–737.3 and 3–118.1 lg/l in dry and wet season, respectively. The extreme value is determined in K3 and K4 samples, which originated from animal reared. Generally, the increase of Zn contents of groundwater is related to agricultural activity in the study area. For Zn ion, health-based guideline value has not been proposed in WHO (2008) standards. But, the permissible limit for Zn is purposed in the EPA (2012) standards as 5,000 lg/l. The Zn contents of the water sample are within the permissible limit of EPA (2012).
form ‘‘inorganic’’ compounds, or carbon and hydrogen to form ‘‘organic’’ compounds. Inorganic arsenic occurs naturally in certain types of rocks, sediments and many minerals. The most common minerals are arsenopyrite (FeAsS), orpiment (As2S3) and realgar (As4S4). Sediments derived from volcanic rocks generally have higher arsenic concentrations (Saldivar and Soto 2009). The concentration of the Arsenic in the study area ranged from 3 to 7.3 lg/l in wet season and \0.1–1.6 lg/l in dry season (Table 3). The permissible limit of As for drinking water is 10 lg/l according to WHO (2006, 2008), EPA (2012) and Turkish drinking water (TSE-266 2005) standards. The As concentration of water samples is generally increased in wet season, almost always associated with arsenic-containing bedrock formations such as Kızılcadag˘ me´lange and Elmalı formation. Natural arsenic in groundwater at concentrations above the drinking water standard of 10 lg/l is not uncommon. Factor analyses
Lead (Pb) Lead is widely dispersed in sedimentary rocks. It is widely found in galena, K-feldspar and mica minerals. The decay of K-feldspar and mica minerals which are found in magmatic and metamorphic rocks are the main source of Pb ion in the sedimentary rocks (Sahinci 1991). Concentration of Pb in natural water increases mainly through the anthropogenic activities. Pb contents of groundwater were changed to \0.1–1.6 lg/l and 0.2–4.2 lg/l in dry and wet season, respectively. The Pb content of the water sample is within the permissible limit of WHO (2008) with 10 lg/l. Chromium (Cr) The ultramafic igneous rocks are higher in chromium content than other rock species. In rock minerals the predominant oxidation state is Cr3?. Dissolved chromium, however, may be present as trivalent cations or as anions in which the oxidation state is Cr6?. In alkaline oxidizing solutions, chromate anions may be stable, but some cations form chromates having low solubilities (Hem 1985). Cr concentration of groundwater ranges from 0.9 to 13.8 lg/l in wet season and from 1.4 to 16.1 lg/l in dry season (Table 3). These values are within the permissible limit (50 lg/l) for drinking water of WHO (2006, 2008) and TSE (2005). Concentration of Cr in natural water increases mainly through the anthropogenic activities in the basin. Arsenic (As) Arsenic is a naturally occurring element often combined with other elements such as oxygen, chlorine and sulfur to
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Factor analysis offers a powerful means of detecting such similarities among the variables or samples. The purpose of factor analysis is to interpret the structure within the variance–covariance matrix of a multivariate data collection. The technique which it uses is extraction of the eigenvalues and eigenvectors from the matrix of correlations or covariances (Davis 1973). Thus, factor analysis is a multivariate technique designed to analyze the interrelationships within a set of variables or objects (Belkhiri et al. 2012). Factor analysis as applied to widely differing sets of groundwater hydrogeochemical data appears to be moderately successful as a statistical tool for revealing hydrochemical and hydrogeological features (Mahlknecht et al. 2004). The aim of the factor analysis of the hydrogeochemical data is to explain the observed relationship in simple terms expressed as a new set of variables called factors. Contribution of a factor is said to be significant when the corresponding eigenvalue is greater than unity (Briz-Kishore and Murali 1992). In general, the factor will be related to the largest eigenvalue and will explain the greatest amount of variance in the data set (Srivastava and Ramanathan 2008). R-mode factor analysis was carried on a subset of 20 selected variables (pH, EC, TH, Na?, K?, Ca2?, Mg2?, Cl-, SO42-, HCO3-, NO3-,NO2-, NH4?, Mn, Cu, Zn, Pb, As, Fe, Cr), which represent the overall geochemical framework. For dry period, the first five factors show eigenvalues [1; thus these five factors were chosen. In the wet period, six factors have eigenvalues [1; thus six factors were chosen for the subsequent factor extraction (Table 4).
Environ Earth Sci
Dry season
Table 4 Factor loadings from R-mode factor analysis July 2012 (Wet period) Factor 1
Factor 2
Factor 3
Factor 4
Factor 5
Factor 6
Na?
0.602
0.025
0.414
-0.114
0.594
K?
0.542
-0.118
0.032
-0.469
-0.245
0.149
Ca2?
0.334
-0.188
0.210
-0.294
0.032
0.709
Mg2?
0.881
-0.084
0.160
0.147
0.206
-0.293
Cl-
0.325
-0.151
0.858
0.135
-0.107
0.221
SO4
0.328
-0.293
-0.139
0.024
0.803
0.012
HCO3TH
0.951 0.854
-0.024 -0.107
0.088 0.375
-0.063 0.001
0.199 0.222
0.116 0.225
EC
0.742
-0.157
0.447
-0.040
0.337
0.218
pH
-0.266
0.182
-0.547
0.647
-0.165
0.019
NH4?
-0.163
-0.224
0.291
0.735
-0.104
-0.227
NO2
-
0.272
-0.203
0.396
-0.289
0.120
0.565
NO3-
0.172
0.167
0.881
-0.005
0.180
-0.084
Mn
0.192
0.212
0.203
-0.134
0.877
0.091
Cu
0.153
0.923
-0.010
0.118
0.106
0.026
Zn
-0.256
0.712
-0.089
-0.059
-0.147
-0.328
Pb
-0.214
0.909
0.025
-0.003
0.067
-0.166
As
0.264
0.070
-0.060
0.921
0.007
0.063
Fe
-0.019
0.422
0.080
0.584
0.659
0.110
Cr
0.346
0.155
0.244
-0.307
-0.038
20.787
2-
-0.057
Factor 1 of the principal component factor matrix of groundwater in the C¸eltikc¸i plain is characterized by the strong loading of Mg2?, HCO3-, SO42-, TH, Fe, Cr in dry season (39.58 % of the variance). The strong loading of HCO3- ions with alkali and alkaline earth metals supports the view of natural weathering sources. The strong loading of Mg2?, SO42-, Fe and Cr represents sediment water interaction and weathering process. The association of K?, Ca2?, Pb in Factor 2 explains 16.87 % of the total variance in the season. The loading of K? and Ca2? indicates natural weathering of rock minerals and various ion-exchange processes in the groundwater system in the study area. The elevated level of rotated factor loading shows that Pb indicates anthropogenic input in the groundwater system. Factor 3 is characterized by strong loading of Na?, Mn, Cu and Zn which accounts for 12.73 % of total variance in dry season. The strong loading of Na? and Mn indicates natural weathering of rock minerals and various ionexchange processes in the groundwater system in the plain. Cu and Zn are associated with agricultural activities. Factor 4 and Factor 5 indicate an increase of NO3-, NO2-, NH4? and Cl- ions suggesting an anthropogenic pollution (Table 4).
October 2012 (Dry period) Factor 1
Factor 2
Factor 3
Factor 4
Factor 5
Na
0.553
0.088
0.684
-0.319
0.280
K?
-0.041
0.659
0.488
-0.504
0.199
0.063
0.891
0.187
0.312
0.184
?
Ca2? Mg
2?
0.911
0.223
0.007
-0.241
0.197
ClSO42-
0.025 0.772
0.237 0.176
-0.012 0.423
0.089 0.158
0.886 0.202
HCO3-
0.606
0.309
0.244
-0.089
-0.232
TH
0.601
0.340
0.131
0.064
0.245
EC
0.576
0.584
0.306
-0.031
0.478
pH
-0.004
-0.435
-0.613
-0.186
-0.420
NH4?
0.041
0.116
0.043
0.970
0.084
NO2-
0.041
0.116
0.043
0.970
0.084
NO3-
0.044
0.050
-0.015
0.003
0.972
Mn
0.386
0.001
0.902
0.030
0.069
Cu
-0.102
0.482
0.753
0.122
-0.207
Zn
-0.100
0.387
0.837
0.071
-0.156
Pb
-0.022
0.899
0.208
0.092
0.172
As
0.561
-0.183
-0.157
0.168
-0.144
Fe
0.755
0.121
0.340
0.261
-0.243
Cr
0.636
-0.035
-0.261
-0.496
0.195
Factor loadings of the rotated solution of principal component analysis (R-mode factor analysis). Variables displaying significant weights on the extracted factors are in bold
Wet season Factor 1 is characterized by strong loading of Na?, Mg2?, HCO3-, TH and EC which accounts for 34.66 % of the variance in wet season. The strong loading of Na?, Mg2? and HCO3- indicates carbonate weathering reactions and ion-exchange processes in the groundwater system in wet season. Factor 2 of the principal component factor matrix of groundwater in the C ¸ eltikci plain is characterized by the strong loading of Cu, Zn and Pb ions which accounts for 16.89 % of the variance in wet season samples. The Cu, Zn and Pb ions probably resulted from anthropogenic input such as animal reared and agricultural activities in the groundwater system. Factor 3 is characterized by strong loading of Cl and NO3- which accounts for 12.74 % of total variance in wet season and Factor 4 includes pH and NH4? which accounts for 8.95 % of total variance. The strong loadings indicate an anthropogenic input in the groundwater system due to leaching of fertilizer from agriculture land and groundwater chemistry is controlled by the pH variation in the aquifer system. Factor 5 and Factor 6 are characterized by the SO42-, Mn, Fe, Ca2? and Cr which accounts for 7.89 and 6.16 % of total variance, respectively. The increases of ions are related to water– rock interaction and weathering process (Table 4).
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Environ Earth Sci Fig. 9 Plot of d2H and d18O compositions of groundwaters
Stable isotope Stable isotopes are useful in groundwater applications which include studies of recharge and discharge processes, flow and interconnections between aquifers, and the sources and mechanism of pollution. The stable isotope analyses were made in July 2012. The deuterium content of groundwater from the C¸eltikc¸i Plain ranges from -43.37 to -59.07 and the values for d18O range from -6.59 to -9.25 with respect to SMOW (Table 3). The relationship between the d18O and dD values of groundwater samples is plotted in Fig. 9, which also shows the global meteoric line (dD = 8 d18O ? 10) of Craig (1961) with d-excess value of 10 % and the meteoric water line of Lake District of Turkey (dD = 8d18O ? 14.6) of Dilsiz (2006) with d-excess value of 14.6 %. Groundwaters from the study area show nearly similar isotopic compositions suggesting similar recharge conditions. All of the groundwater sample plots on the Global meteoric line indicate its meteoric origin. It is affected by Global precipitation. The d18O shift of some groundwater samples (K1, K4, K5) indicate water– rock interactions and a recharge altitude effect. The degree of the shift depends on residence time of water and rock– water interaction (Truesdell and Hulston 1980). Groundwaters collected from the study area show a deuterium excess (d-excess = d2H-(8 9 d18O) higher than 10 % (ranges from 10.71 to 18.02 %; Table 3). These isotopic features suggest that most of the groundwaters results from a mixing between recent recharge and an older component recharged under climatic conditions cooler than at present. Tritium concentrations in groundwater may be used as indicators of groundwater age. The tritium level in young
123
groundwater is about the same level as in precipitation. Since the mid-eighties the tritium values in rain water are 10 TU in the northern hemisphere (Mook 2001), except for some local anthropogenic releases of tritium from the nuclear industry. As the water moves downward and laterally, the tritium concentration decreases with time. Without monitoring tritium in the precipitation in the region, we used a mean value of 10 TU given by the IAEA. The water samples with tritium contents between 2.59 and 4.53 TU indicate a mix of submodern and modern water. So, the groundwater included both circulating waters which represented water–rock interaction within the aquifer and a modern water contribution which can be included contamination parameters related to land use.
Conclusion Groundwater quality in the C ¸ eltikc¸i plain is strongly influenced by water–rock interactions and anthropogenic activities. The rock dominance of the major ion chemistry in the basin provides an insight of chemical weathering in the drainage basin, since weathering of different parent rocks (e.g., carbonates, silicates, and evaporites) yields different combinations of dissolved cations and anions to solution. The water composition is controlled by the composition of sedimentary rocks in the basin and hydrologic characteristics such as the flow path and residence time. The geological framework and spatial repartition of chemical elements indicate an origin controlled by the dissolution of carbonate rocks. The groundwaters are freshwaters and the dominant water types are Ca–HCO3
Environ Earth Sci
and Ca–Mg–HCO3. According to R-mode factor analyses results and hydrogeochemical evaluations, natural weathering of rock minerals and various ion-exchange processes are fundamental natural factors controlling hydrogeochemical processes in the study area. Besides, anthropogenic input is effective on the groundwater hydrogeochemistry in the plain. The d18O, dD and tritium values of groundwater samples indicate a mix of submodern and modern water. Quality assessment shows that, in general, the waters are suitable for potable, domestic and irrigation purposes. However, high values of TH, NO3 and Mn contents at some sites make them unsafe for drinking and domestic purposes. According to Na%, SAR, USSL classification and Wilcox classification, RSC and MH values of the groundwater are suitable for irrigation, but PI values of the waters are unsuitable for irrigation. The increases of Mn, Fe and As concentrations are related to water–rock (Elmalı formation) interaction. NO3-, Pb, Zn, Cr and Cu concentrations are increased related to anthropogenic origin such as agricultural activity and animal reared. Overall, groundwater quality in the C¸eltikc¸i plain is impeded by anthropogenic activities, and proper groundwater management strategies are necessary to protect sustainably this valuable resource. Acknowledgments This work was supported by the Research Fund of the Su¨leyman Demirel University. Project number: 3087-YL-12. ¨ zgu¨l, Geological Eng. The support of Geological Eng. E. Birol O Hu¨dai Manga and Technician Ahmet Ali C¸ankaya from the State Hydraulic Works (SHW) XVIII Regional Directorate, Isparta is gratefully acknowledged.
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