Hydrogeochemical evaluation of Western Anatolian mineral waters

Original article

Hydrogeochemical evaluation of Western Anatolian mineral waters I.F. Barut Æ N. Erdogan Æ E. Basak

Abstract Turkey lies on the Alpine-Himalayan belt which is one of the most important geothermal belts in the World. Therefore, there are numerous mineral waters in Anatolia where geological and tectonic activities are intense. Archeological studies conducted in Anatolia, which is the cradle of various civilizations, reveal the fact that mineral water has been used as a spa in many areas. The scope of this study is to evaluate mineral waters in Western Anatolia and their use in thermal resorts for balneological purposes. In this respect, 50 thermal waters used in spa centers were analyzed for various physical, chemical and bacteriological parameters. Among the 50 waters tested, 40 are thermomineral waters while 10 are acratothermal waters. Some of these waters have distinct chemical compositions. Their temperatures are between 21 and 90 C. Various types of mineral water source occur within this region: 5 of these are sulfurous, 1 has carbon dioxide, 29 have fluorine, 1 has iodine and 3 are saliferous. The thermomineral sources with saline characteristics have balneotherapy potential for treating skin illnesses including psoriasis and rheumatological illnesses. Some waters with appreciable bicarbonate and sulfate concentrations can also be used for balneotherapy; for example for use as a cure for chronic inflammatory diseases of gastrointestinal and urinary systems. They could also be used as a

Received: 18 October 2002 / Accepted: 31 August 2003 Published online: 29 October 2003 ª Springer-Verlag 2003 I.F. Barut (&) Istanbul University, Institute of Marine Sciences and Management, Mu¨s¸ kile sok., Vefa, 34470 Istanbul, Turkey E-mail: [email protected] Fax: 0212 2304469 N. Erdogan Æ E. Basak Medical Faculty, Medical Ecology and Hydroclimatology Department, Istanbul University, Istanbul, Turkey

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cure for prophylactic and metaphylactic treatment of urolithiasis. However, among 38 sampling sites, 12 sites are bacteriologically contaminated. This indicates that regulations governing the protection of such zones are not properly enforced and that water sources within these regions are not sufficiently protected or inspected. Keywords Western Anatolia Æ Mineral waters Æ Hydrogeochemical Æ Balneological evaluation

Introduction Active tectonism in Anatolia have produced various geological structures which explain the presence of numerous hot springs and cold mineral waters with varying temperatures and chemical compositions. Archeological studies performed in Anatolia, which is the cradle of various civilizations, reveal findings of interest regarding the use of mineral waters. Many of the baths in the region are derived from the Roman, Seljuk, Byzantium and Ottoman Empires and are still in use today. Western Anatolia has undergone intense tectonic activity. The numerous hot springs in this region are used for tourism and balneotherapy purposes. In this study the authors will make some suggestions for the use of mineral waters and spa tradition is studied scientifically. In this respect, the Istanbul University Research Fund supported a research project. Within the frame of this project, a total of 50 water sampling sites were selected, namely in Afyon (site number 3, Fig. 1), Aydin (3), Denizli (7), Izmir (9), Kutahya (15), Manisa (9), Mugla (2), and in Usak (2). Distribution of water sampling sites is shown in Fig. 1. Geographic distribution of mineral waters is generally affected by neotectonic horst and graben systems developed as a result of active tectonism in the Aegean region.

Sampling and field studies In this study, thermal waters were sampled in different periods between 1991 and 1999. Nineteen waters were

DOI 10.1007/s00254-003-0904-0

Original article

Fig. 1 Location of Western Anatolian mineral waters (see Table 1, for the localities matching the reference numbers)

sampled from drill holes, 1 from a bathtub, 1 from the water supply to houses and 29 from springs. Total mineralization and temperatures of the sampled waters are presented in Table 1. Regarding the physical and chemical analyses, all samples, except one were sampled on the basis of procedures in the American Public Health Association’s ‘‘Standard methods for the examination of water and wastewater’’ (APHA and others 1989). The sampled waters were collected in 500-ml polyethylene containers each of which had been washed at least three times with the sample water. If the sampling point was a well, the mineral water was allowed to run for ten minutes before the sample was taken, on the basis of water discharge and production depth. Temperature and pH were measured at the sampling site with a HACH brand pH meter. Electrical conductivity (EC) of samples was measured using an YSI brand 33 S-C-T conductivity meter. Salinity and temperature values were also checked with the same instrument. Sulfur (S2)), ammonium (NH4+), nitrate (NO3)), nitrite (NO2)), phosphate (PO43)) and iron (Fe2+) concentrations were analyzed at the sampling site with a HACH DR 2000 spectrophotometer while carbon dioxide was analyzed using a titration method. For heavy element analysis, a sample was taken by reducing the water pH to 2 with nitric acid (HNO3) and back in the laboratory, the measurement was made with HPLC. Sodium (Na+) and potassium (K+) concentrations were determined with Eppendorf brand flame photometry. Halogens were measured with Orion model 407 A selective electrodes. Chloride (Cl)), calcium (Ca2+) and magnesium (Mg2+) were analyzed with the titration method. Arsenic was measured with the silver diethil carbonate method.

Sulfate (SO42)) was measured with the nephelometric method. For the microbiological analysis, water samples were sterilized at 170 C. After sterilization the samples were placed into a 750 ml glass jar. The water samples were stored at +4 C, the parameters measured include the total number of bacteria in 1 ml, coliform bacteria in 100 ml, fecal coliform in 100 ml, and Pseudomonas aeruginosa. The sample is mixed on a petri dish with Plate Count Agar nutrition at 22 C and stored at 37 C for 48 h. Every colony is considered as potential bacteria. The coliform bacteria are observed by the technique of multiple fermentation in lactose broth (oxoid) nutrition at 37 C and after 48 h the formation of gas in Durham bottles indicates the formation of bacteria. At the end of this 48 h period, the most probable number in 100 ml is recorded. By the inoculation from Lactose Broth to EC Broth the fecal coliform number in 100 ml is indicated and by the inoculation to Pseudomonas Agar the presence of Pseudomonas aeruginosa is recorded. The results of the microbiological analyses are checked with critical threshold values given in the ‘‘Criteria of natural source, drinking water and medical waters’’ (Dogal Kaynak, Maden ve Içme Sulan Ile Tibbi Sulann Istihsali, Ambalajlanmas ve Satisi Hakkinda Yonetmelik 1997).

Regional hydrogeology The general orientations of old structure systems in the region are characterized by paleotectonic evolution and


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Table 1 Chemical composition of the Western Anatolian mineral waters

Number

1 2 3 4 5 6 7

Country

Afyon Aydin Denizli

8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

_ Izmir

Ku¨tahya

26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

Manisa

41 42 43 44 45 46 47 48

Mug˘la

49 50

Usak

Name

Orucog˘lu-1 Orucog˘lu-2 Hayat Alangu¨llu¨-k Alangu¨llu¨-dww Davutlar Colossea-hot dww Colossea-cold dww Karahayit-red water Richmond-1 Richmond-2 Richmond-3 Yenicekent Aliaga-ilicaburun Bademli-gu¨ltas Balcova-y Vardar Cumali Kinik-hasar Princess-eç Princess-eg Princess-room Emet-e Emet-y Emet-greenspring Dereli-e Dereli-incirli Dereli-magara Hamamkoÿ Sefakoÿ-1 Sefakoÿ-2 Yoncaag˘ac-e Yoncaag˘ac-karandere Yoncaag˘ac-kh Ilicakoÿ Ilicakoÿ-go¨kkurna Go¨bel Alasehir Demirci-1 Demirci halikent Kavaklidere Salihli-sart Turgutlu-urganli Horzumsazdere Baklacidere Turgutlu-urganli-e Dalyan-ae Dalaman-ku¨ku¨rtlu¨go¨l Banaz ¨ rencik O

N-S compression of Western Anatolia. Whereas, young structure systems in this region are characterized by neotectonic evolution and a N-S distribution of lineaments. As a result of the neotectonic activity, some important fault zones and graben systems were 496


Type

Total mineralization (mg)

Temperature (oC)

Drilled well water Drilled well water Drilled well water Spring water Drilled well water Drilled well water Drilled well water

2,745 3,296 3,113 4,938 5,305 5,003 3,098

49 41 51.1 59.2 48.6 41.2 34

Drilled well water

3,036

30

Spring water

3,046

51

Drilled well water Drilled well water Drilled well water Drilled well water Spring water

2,764 2,770 2,693 2,918 21,824

47.8 47.6 46.1 34 51.4

Drilled well water Drilled well water Spring water Spring water Spring water Drilled well water Drilled well water Bathtub Spring water Spring water Spring water-stream

8,319 1,440 1,085 17,901 1,673 1,342 1,321 352 499 521 551

59 90 42.1 58.2 21 55 65 50 47 42 42

Spring water Spring water Spring water Spring water Spring water Spring water Drilled well water Spring water

1,211 1,201 1,202 958 896 836 1,459 1,638

38.4 38.8 38.8 44 51.5 41 50.5 38

Spring water Spring water Spring water

1,398 814 708

46.5 42.3 42

Spring water Drilled well water Drilled well water Drilled well water

524 4,395 2,309 2,086

32.8 36.5 46.5 36.7

Drilled well water Spring water Spring water

5,467 1,803 2,300

48.5 52.1 62.2

Spring water-stream Drilled well water Spring water

3,540 4,394 2,365

29.7 30.2 54.3

Drilled well water Spring water

30,444 18,203

37.5 27

Spring water Drilled well water

5,160 4,472

59.5 39

developed in Western Anatolia. In Western Anatolia, there are a vast number of Neogene occurrences that developed in basins of different size. These Neogene sediments are generally terrestrial facies (lacustrine or volcanic).

Original article

Fig. 2 T(C) characterization of mineral waters

Menderes Massif is exposed in most parts of the Western Anatolia and has an area of 200·300 km and consists predominantly of metamorphic rock series. Gediz, Kuçuk, Buyuk Menderes, Akcay and Cine Rivers run through the Menderes Massif. The northern and eastern boundaries of the massiv are not distinct. The Menderes Massif is surrounded by the West Taurids to the south and the IzmirAnkara ophiolite belt to the east. The width of the massif is 200 km between Mugla and Simav and 150 km between Denizli and Turgutlu. To the south of Menderes Mountain lies the SW Anatolian Taurid mountains. They are formed from an ancient nucleus and have a SW-NE alignment. They are covered by a range of detrital and carbonaceous rocks and form a dome. To the south of the dome there are inverted folds, which continue along the Aegean coast (Graciansky 1965). Earlier researchers (Graciansky 1965, 1972) described the rocks of the massif as an ‘‘AUTOCHTHON’’, an ‘‘ALLOCHTHON’’ and a ‘‘NEO-AUTOCHTHON’’.An autochthon sequence consists of a nucleus of gneiss and migmatite rocks overlain by covering groups of various schist units, Permian, and Paleocene calcareous sediments. The Allochthon sequence is formed by Paleozoic and Mesozoic sediments. They are also called the Tauros Belt. This allochthon band has a neotectonic contact with the Menderes Massif (Akat and others1975). In some places within the region the autochthon and allochthon groups have some similarities. However, Late Paleocene red limestones around MilasMugla are believed to be a key bed for distinguishing the autochthon and allochthon series (Barut 2001). According to regional hydrogeologic observations, thermal waters in the region generally issue through fault zones and from the faults that form the graben systems. Marble, calcschist and quartzite zones within the metamorphics of the Menderes Massiv (marble, calc-schist, quartzite, various schist and gneiss units) are permeable and they form the most important thermal water aquifer. A number of thermal waters can be explained in this way are Afyon-Omer-Gecek, Denizli-Yenice (13, Fig. 1), Karahayıt (9), Manisa-Salihli Alasehir (42), Usak, Izmir-Bayındır and Kutahya. Paleozoic formations contain clayey schist, meta-sandstones and crystalline limestones. Meta-sandstones and crystalline limestones comprise the main aquifer. Pliocene volcanites, Quaternary alluvium and molasse deposits are

observed in recharge areas. The formation of Izmir-Balcova (16) thermal springs can be explained in this way. Neogene claystone, marl, limestone and volcanic units including andesite, basalt and agglomerate are widely exposed in Denizli-Karahayıt, Afyon and Izmir-Balcova basins. In the Afyon and Denizli geothermal areas, limestones and basalts comprise the main reservoir. The overlying Travertine deposits and Quaternary alluvium units consist of sand, clay and conglomerate are believed to be the secondary reservoir where cold groundwater and thermal waters are mixed. In addition to these aquifer units, fault zones were also important conduits for water circulation. In the Mugla region, from Datca peninsula at MarmarisKoycegiz and Fethiye at Denizli-Burdur, Acıpayam, GolHasar, and Tefenni, the plutons consist of peridotites with small volumes of pyroxenite, dunite and gabbro. Around Izmir, Manisa, and Usak there is evidence of volcanism originating from the Miocene, Pliocene, Pleistocene, and continue into the Holocene (Ercan 1979). All thermal waters being studied were formed by the heating of deeply circulating meteoric water within the geothermal gradient and their rise to the surface has been through faultfracture zones. Besides spring waters in Afyon, Izmir, Kutahya, Usak, Denizli and Aydın, the water production in these areas was increased by drilled wells. Natural spring waters are used only in the Manisa-Salihli-Sart and Turgutlu-Urganlı fields (Turkiye Jeotermal Envanteri 1996). Paleozoic marble, quartzite, calc-schist and Neogene limestone and basalts are the primary aquifers in the region. Graben-forming fault and fracture zones in each area are also important aquifer zones for the circulation and storage of waters.

Physical and chemical characteristics of waters Temperature (T) Waters of the Aegean region are classified as thermal waters. Water temperatures of springs and wells are between 21 and 90 C (Fig. 2). Temperatures of the studied


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and carbonate-sulfate waters with very high carbonate waters are as follows: (1) 8 mineral waters with T 100 FrS; Fig. 1) differ from the others. This might be due to the – 3 mineral waters with a hardness of 0.1 with crusting mineralized waters. TDS values of waters are as follows: potential; – 1 mineral water with TDS content of >30,000 mg/l; – 24 mineral waters have SI values Ss.

The difference with (pH—pHs) and SI is explained by the fact that the ions in the surroundings are higher than the pH values calculated. This explains the high concentrations of CO3 and HCO3 in the environment and the formation of CO2 by CO3, HCO3 changing the acidic and basic properties. This difference can be explained by temperature, the contact time with O2 by the effect from other ions. This result supports the alimentation by the system at a low level. SI positive values are an indicator of CO3 increase. The general classification of associated rocks is evaluated as the rocks containing CO3. SI negative waters indicate that the ground waters are affected by the acidic properties of the environment. The waters relate to rocks containing SO4. The environment is characterized by gypsum and epsomite.

Fig. 8 Chemical compositions (Na, Ca, Mg, Cl, SO4, HCO3) characterization of mineral waters

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Fig. 9 Hydrogeochemical classification Schoeller diagram of mineral waters according to countries

Statistical analysis A statistical analysis has been conducted in order to determine the chemical composition of Western Anatolian mineral waters and the interaction between rocks and water. The relationships between anions and cations of sampling points, the total mineralization and the effect of temperature have been analyzed using the SPSS (SPSS for Windows release 10.0.1, 1999, standard version) program. The results are as follows:

Ca, Mg and SO4, and the second factor is Na, and Cl. The cumulative value of these 2 factors is 83%. We can conclude that the division by groups is significant statistically. For the rock-water interrelation the first group is formed by the waters with Ca, Mg and SO4, while Na and Cl waters form the second group. All sampling points have a relationship with the second factor. The lithology sampling points and the physical and chemical properties of waters are evaluated together. The first group of waters is affected by calcareous rocks, dolomites and marl. The second group is formed by the coastal aquifers and mixed with saline waters.

– For the relationship between the temperature and the total mineralization, the regression analysis is realized but a significant effect was not observed (r‡0.038); – For the chemical composition the correlation analysis is realized for Na, Cl, Ca, Mg with SO4. A reasonable correlation is obtained between Mg and Ca. (r‡0.5) – Within factor analysis the variance of anion and cation are separated according to two factors; the first factor is

The microbiological content of waters Among 38 sampling points, 26 are drilled wells and 12 are natural thermomineral spring waters. The results of the analysis show that in 4-drilled wells and in 8 natural spring waters bacteria are observed as an indicator of pollution. The thermomineral waters, which are not in agreement with the microbiological standards, are:


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Fig. 10 Sc-Ss to establish mineral water relationships

Fig. 11 EC-pH to establish mineral water relationships

Fig. 12 CO2 contents of mineral waters

– – – –

Afyon-Orucoglu II (2) Aydın-Kusadasi Davutlar (6) Izmir-Dikili Hayıtlı (15) The room of Balcova Princess Otel (22).

Conclusions and discussion

1. The most important aquifers in the region are formed by Paleozoic marble quartzite, calc schists and Neogene limestone and basalts. Grabens provide the aquifer The natural thermomineral spring waters, which are not in regions, where thermal waters are stored. agreement with microbiological standards, are: 2. The low level of Ca (Mg) and HCO3 ion concentrations and high pH accelerate calcite precipitation (Duchi and – Denizli-Karahayıt Red water and Yenicekent (9 and 13) others 1991). Therefore, calcite is rapidly precipitated _ Aliaga Ilıcaburun (14) – Izmirin Izmir-Kınık Hasar water and in Izmir-Kınık Hasar – Kutahya-Emet, Gunluce Dereli and Magara springs (23, suyu. 26 and 28) 3. In rocks of anhydrite-carbonaceous aquifers, in cold– Manisa- Alasehir Horzum Sazdere (38) water circulation, Ca2+-Mg2+ and HCO3)-SO42) ion – Turgutlu-Urganlı (46)

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groups are separated. Considering the Cl species, during the water circulation in aquifer and fine-grained marine Neogene sediments, syngenetic waters are mixed with percolation. 4. High CO2 concentration in waters is attributed to the fact that the region is affected by active tectonism (Fig. 12). The presence of SiO2 in carbonate minerals indicates that CO2 is formed via a decarbonation process (Fyfe and others 1978) but not in low temperature conditions (