Original article

The impact of hydrological changes on travertine deposits related to thermal springs in the Pamukkale area (SW Turkey)
Manuel Marques Paula Maria Mimo Carreira neyt Dilsiz Jose Cu Abstract Pamukkale thermal waters (35 C), exhibiting calcium-bicarbonate-sulfate composition and high carbon dioxide concentration, are of a predominantly meteoric origin. The meteoric uid, circulating through faults and fractures, is heated by magmatic intrusions at great depth, and ascends from deep reservoirs to the surface. Mixing with relatively cold groundwater in the near surface zone promotes different saturation conditions with respect to calcium carbonate that later precipitates at depth and/or the surface. Dissolution-deposition processes of calcium carbonate both at surface and depth environments may help to reconstruct past climate direction in the eld. During wet climate conditions a high-rate of calcium carbonate accumulation would be expected to occur at the surface because thermal uid would be undersaturated with respect to calcium carbonate at depth because of a relatively higher mixing ratio with cold groundwater. During dry climate conditions the thermal uid would be super-saturated at depth because of the highly acidic environment. Hydrometeorological studies reveal that the annual precipitation at the Pamukkale hydrothermal eld tends to decrease with time. This climatic change in the area was also detected from geological records. While humid climate conditions prevailed during the late Quaternary, the area has recently been affected by arid/semi-arid climate conditions, followed by some episodic transitions. This study has shown how the system has possibly reacted to different climate conditions since antiquity. Keywords Travertine deposit Thermal spring Hydrology Climate Pamukkale

Introduction
This paper describes recent research studies performed at Pamukkale hydrothermal eld, southwest Turkey (Fig. 1), in order to identify the response of the Pamukkale hydrothermal system to climatic change. In scientic literature, travertine is used to describe a calcium carbonate deposit (e.g. Panichi and Tongiorgi 1975; Dramis and others 1999) that is precipitated from super-saturated thermal and fresh waters, with respect to calcite. The deposition of calcium carbonate both at surface and depth conditions occurs during the carbon dioxide degassing, responding to a decreasing of carbon dioxide partial pressure and an increase of carbonate ions. Travertine resulting from the thermally generated carbon dioxide is described as thermogene travertine by Pentecost (1995). At the Pamukkale site, the thermal springs produce a distinctive type of thermogene travertine, which has been attracting the attention of people; travertine deposition has been progressing since the late Pleistocene (Engin and others 1999). Past hydrothermal circulation in the eld is evidenced by the existence of calcium carbonate-lled fractures or veins, through which hydrothermal uids once owed, and travertine deposits around fossil spring outlets. Travertine formation may help to predict the direction and/or the magnitude of the modications in the hydrological variables as the result of local climatic changes. The aim of this paper is to interpret calcium carbonate dissolution-precipitation processes associated with the evolution of Pamukkale thermal uids, in relation to past

Received: 9 March 2003 / Accepted: 11 November 2003 Published online: 15 January 2004 Springer-Verlag 2004
C. Dilsiz (&) Faculty of Earth and Life Sciences, Vrije University, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands E-mail: dilsiz@hotmail.com Fax: +31-20-6462457 J.M. Marques Laboratory of Mineralogy and Petrology, cnico, Technical University of Lisbon, Instituto Superior Te Av. Rovisco Pais, 1049001 Lisbon, Portugal P.M.M. Carreira gico e Nuclear, Sector Qu mica, Instituto Tecnolo Estrada Nacional n10, 2686953, m, Portugal Sacave

808

Environmental Geology (2004) 45:808817

DOI 10.1007/s00254-003-0941-8

Original article

Fig. 1 Location map

with carbon dioxide (e.g. thermal waters) contact with a climate changes. Though considerable geohydrological information is available on the Pamukkale area, this is the carbonate mineral, then reaction (6) will occur; rst such study to be performed on the travertine deposits, 6 contributing to an update of knowledge on the Pamukkale H2 O CO2 CaCO3s $ Ca2 2HCO 3 hydrothermal system. and this plays a very important role in controlling the geochemical signature of thermal uids. Equations (2) and (4) explain the distribution of the carbon dioxide dissolved in water, which is graphically displayed in the literature in State-of-the-art the so-called Bjerrum plot (Drever 1997). In such a diaSince the emphasis of the paper is on the impacts of dif- gram, we can observe that the pH in a given solution will be a function of the proportion in which carbonate, ferent climate conditions on the active Pamukkale hydrothermal travertine-forming environment, the prin- bicarbonate and carbon dioxide are present. Based on Eq.(6), it can be stated that if the concentration cipal concepts of the H2O.CO2.CaCO3 system corresponding to travertine occurrences are equally relevant to of dissolved carbon dioxide is less than the dissolved carbon dioxide regulating calcium carbonate equilibrium, that purpose. then precipitation of calcium carbonate will occur. ConAs stated by Hem (1970), carbon dioxide in the atmosidering the reverse case, additional calcium carbonate sphere or magmatic emanations dissolves in water until equilibrium is reached (1), then aqueous carbon dioxide dissolution will be possible (Dramis and others 1999). At the water-atmosphere interface at the springs, the undergoes hydration resulting in carbonic acid (2). concentration of carbon dioxide in the water is controlled CO2g $ CO2aq 1 by equilibration with the atmosphere, a process which is very slow and rarely found in nature (Mercado and CO2aq H2 O $ H2 CO3 2 Billings 1975). Instead of this, non-equilibrium conditions prevail in most cases, either as super-saturation and/or The ionization of carbonic acid, a weak acid referred to by under-saturation conditions. Kehew (2001) as diprotic acid, produces bicarbonate and The saturation index (SI) of a solution (7) with respect to a carbonate ions (3, 4). given mineral (at any pressure and temperature) is dened H2 CO3 $ H HCO3 3 as the ratio between the ion-activity product of the ionic species in solution (IAP) and the corresponding thermo 2 HCO3 $ H CO3 4 dynamic equilibrium constant (K) (Appelo 1988; Dreybrodt 1988); Through the reactions (3) and (4) the pH of the solution is IAP lowered as a result of an increase in hydrogen ion SI log 7 concentration. If an alkaline substance is present, K hydrogen ions will be removed from the solution, allowing The solution is super-saturated for SI > 1 and underthe formation of more bicarbonate. saturated for SI < 1. Carbonate minerals are common alkaline substances and The solubility of a given gas in a known volume of liquid at are dissolved by hydrogen according to the following both chemical equilibrium and constant temperature, is reaction; expressed by Henrys law where the quantity of a dissolved gas is proportional to the gas pressure on the liquid CaCO3s H $ Ca2 HCO 5 3 (Capasso and Inguaggiato 1998); In other words, as shown in Eq (5), the dissolution of calcium carbonate is greatly increased by the presence of KH pi 8 ui hydrogen ions (Trudgill 1985). If water originally charged 809

Environmental Geology (2004) 45:808817

Original article

Fig. 2 A cross-section of Pamukkale hydrothermal eld, presenting tectonics, geology and main groundwater ow patterns

where KH is Henrys constant, pi is the partial pressure of the i-gas in the vapor phase (in atm), and /i is the molar fraction of this particular gas in the liquid phase. Henrys constant depends on the temperature and salinity of the system, as discussed by Capasso and Inguaggiato (1998). Dramis and others (1999) presented the results of a study showing that water at 0 C dissolves about three times as much carbon dioxide as at 30 C, explaining why the solubility of calcium carbonate [corresponding to the carbon dioxide solubility based on Eq. (6)] is inversely correlated with temperature.

multi-layer aquifers composed of carbonate layers of different ages (e.g. Paleozoic marble, Mesozoic crystallized limestone, Pliocene limestone (Pl2 Formation) and Quaternary travertine). Lithological units of claystone, siltstone, marl and sandstone, belonging to the Pl1, Pl3 and Pl4 Formations can locally act as an impermeable caprock in the system (Ozpinar 1994; International Research and Application Center for Karst Water Resources -UKAM1994; Vengosh and others 2002; Fig. 2). The recharge of the regional groundwater system is supplied by meteoric water (Gunay and others 1997). This hypothesis is supported by similar isotopic signatures (deuterium values) presented by the thermal waters and the local meteoric waters inltrated on the highest topography (Table 1). In the study area, the groundwater Site description ow paths between recharge and discharge areas are Pamukkale hydrothermal eld (3755 N, 2907 E), located complicated and controlled by tectonic structures, anisotropy in permeability, thermal gradients and local in southwest Turkey, is a well-known place due to the topography. The hydrogeological conceptual circulation existence of thermal springs and the extensive white model of the Pamukkale hydrothermal system can be travertine accumulations (see Fig. 1). In the region the intense vertical tectonism has modied summarized as follows; (1) inltration of meteoric waters, (2) groundwater-rock interaction leading to the origin of the fracture patterns enhancing the anisotropic permechemicals in the circulating waters and thermal water ability. The hydrothermal system can be considered as
Code Pm1 Pm2 Pm3 Pm1 Pm2 Pm3 Pm1 Pm2 Pm3 Pm1 Pm2 Pm3 Cold spr.1 Cold spr.2 Date 17-Nov-93 17-Nov-93 17-Nov-93 20-Nov-94 20-Nov-94 20-Nov-94 09-Dec-94 09-Dec-94 09-Dec-94 26-Feb-95 26-Feb-95 26-Feb-95 26-Feb-95 26-Feb-95 Temp (C) 35.5 36.0 36.0 36.0 36.0 35.0 35.0 34.5 35.5 36.0 36.0 35.0 10.0 12.0 O-18 (&) )9.29 )9.42 )9.28 )9.00 )9.10 )9.08 )8.91 )8.87 )9.34 )8.87 )9.06 )8.91 )8.45 )8.10 H-2 (&) )59.00 )59.50 )59.30 )59.80 )58.20 )63.40 )59.00 )59.50 )58.00 )59.60 )58.90 )59.70 )56.00 )55.50 H-3 (TU) 4.10 3.30 3.70 4.00 3.60 4.20 4.00 4.30 3.90 4.50 4.10 4.50 17.40 14.80

Table 1 Isotopic composition of thermal and cold springs (cold springs are of seasonal type, meaning a shallow and fast circulation) (data from UKAM 19941996)

810

Environmental Geology (2004) 45:808817

Original article

Fig. 3 Pamukkale plateau. Aerial photography showing thermal spring locations (Pm1, Pm2 and Pm3) and travertine deposits (white area)

occurrence, (3) thermal uid ascension and occurrence of subsurface physico-chemical processes, and (4) surface discharge of mixed waters through springs (see Fig. 2). The discharge of thermal waters takes place along surface representations of the fault systems that appear to follow the northern margin of the Curuksu graben and in the Curuksu valley (at an altitude of 160 m a.s.l.).

Hydrochemistry and travertine formation

Pamukkale thermal waters discharge along a northwesttrending fault mainly in three places; Pm1, Pm2 and Pm3 (Fig. 3). Major ion composition of Pamukkale thermal waters is graphically presented in Fig. 4. The samples, whose electroneutrality meets the condition of 5%, were

chosen. Data were obtained from UKAM (19941996) (Table 2). Pamukkale thermal waters (35 C) are considered to have been derived from the deep reservoir although their chemistry has been modied during upow through boiling and mixing with cold shallow groundwaters (e.g. UKAM 1995, 1996; Gunay and others 1997; Ozler 2000). It is noticeable both from Fig. 4 and the range of temperatures (see Table 2) that the physical and chemical characteristics of Pamukkale thermal waters have remained slightly constant through time, suggesting an equilibrium condition at some points in the system (e.g., Grasby and others 2000). All thermal waters are calcium-bicarbonatesulfate type, resembling immature waters described by Giggenbach (1988). At the outlets carbon dioxide gas bubbles can be clearly observed. According to helium isotope analysis, magmatic emanations are the gas source in the Pamukkale hydrothermal system (Vengosh and others 2002). In previous works performed on the region, no lithological units have been identied as responsible for the high sulfate concentration in the aqueous system (see Table 2). One possible explanation could be related with the oxidation of hydrogen sulde gas component added by the degassing of the heat source. Chloride is not a major component in the thermal waters (see Table 2), and its presence could likely derive both from rainfall itself and/or anthropogenic contamination. Major ion activities and saturation indices (with respect to calcite, aragonite, dolomite, anhydrite and gypsum) were calculated by using the PHREEQC-2 (v.2.5) computer program (Parkhurst and Appelo 1999). The calculations reveal that the Pamukkale thermal waters emerging through the local travertine deposits, are slightly saturated with respect to calcite and aragonite minerals (Fig. 5). The calculated carbon dioxide partial pressure values (using the PHREEQC-2 model) are extremely high, ranging from 0.12 to 1.16 atm, which are far above the atmospheric value (PCO2=0.0003 atm). Such high PCO2 values could be regarded as a signature of the different subsurface physical and chemical processes (e.g., gas-water-rock interactions, mixing, boiling) experienced by the thermal waters discharging in the Pamukkale area.

Fig. 4 Relative amounts of chemical constituents in Pamukkale thermal waters

Environmental Geology (2004) 45:808817

811

812
Original article pH TDS EC Ca+2 Mg+2 Na+ K+ Cl SO42 HCO3 35.8 35.8 34.8 34.5 36.0 35.1 35.0 35.5 35.5 34.8 34.5 34.5 35.8 34.7 35.6 36.0 35.0 34.5 35.0 34.7 35.0 35.6 34.8 35.0 36.5 34.9 35.5 34.0 34.2 34.0 36.5 35.2 0.6 6.2 6.2 5.9 6.5 6.1 6.3 6.2 6.1 6.3 6.0 6.1 6.1 6.2 5.8 6.3 6.1 6.2 6.2 6.0 6.0 6.2 6.2 5.8 6.6 7.0 6.2 6.1 7.0 6.0 5.8 7.0 6.2 0.3 2,820.0 2,880.0 2,850.0 3,000.0 2,850.0 2,890.0 2,800.0 2,550.0 2,800.0 2,730.0 2,670.0 2,880.0 2,780.0 2,850.0 2,830.0 2,820.0 2,860.0 2,800.0 2,800.0 2,700.0 2,830.0 2,890.0 2,850.0 2,800.0 2,900.0 2,890.0 2,850.0 2,800.0 2,790.0 2,550.0 3,000.0 2,821.3 79.9 434.1 435.1 435.1 449.9 535.1 512.4 492.6 469.9 452.5 410.0 525.1 455.9 419.8 430.1 443.1 494.0 514.8 500.0 490.0 392.0 461.9 469.9 425.0 448.9 390.0 517.4 505.0 477.6 401.0 390.0 535.1 457.6 42.9 88.0 84.0 79.9 94.9 89.9 89.9 75.0 87.5 89.9 75.9 99.9 85.9 81.9 84.9 84.0 84.9 99.9 77.4 87.5 75.0 86.9 61.8 79.9 77.9 82.4 89.9 77.4 94.9 75.9 61.8 107.4 85.3 9.0 45.1 30.1 80.0 87.6 83.0 34.9 30.1 34.9 37.5 38.4 36.8 54.9 48.0 84.8 54.0 85.1 34.9 34.9 27.6 38.6 50.1 63.0 80.0 54.0 37.5 42.5 42.5 32.4 38.6 27.6 87.6 50.2 18.8 27.4 27.4 30.1 84.8 45.0 57.5 17.6 27.4 42.6 5.1 5.1 21.9 16.0 55.1 23.8 55.1 75.1 42.6 32.4 7.0 84.8 55.1 10.2 37.1 119.6 19.9 57.5 42.6 7.0 5.1 119.6 38.5 26.7 21.3 10.6 14.2 16.0 24.8 8.9 10.6 17.7 12.4 14.2 17.7 17.7 14.2 17.7 14.2 21.3 14.2 14.2 17.7 10.6 42.5 14.2 14.2 16.0 14.2 14.2 10.6 7.1 14.2 7.1 42.5 15.8 6.2 621.6 652.3 601.9 693.6 700.3 709.0 639.4 727.7 621.6 566.9 558.7 616.8 642.7 564.5 575.5 717.1 691.7 666.7 727.7 580.8 611.0 641.3 591.8 575.5 688.3 713.8 618.7 731.0 590.9 558.7 824.6 653.9 69.9 1,232.2 1,189.5 1,122.4 1,171.2 1,213.9 1,171.2 1,256.6 1,195.6 1,149.9 1,137.0 1,166.3 1,311.5 1,134.6 1,134.6 1,250.5 1,201.7 1,152.9 1,244.4 1,207.8 1,077.9 1,299.3 1,183.4 1,110.2 1,250.5 1,189.5 1,171.2 1,274.9 1,226.1 1,095.6 1,043.1 1,311.5 1,182.5 65.4 2,469.5 2,429.0 2,363.6 2,598.0 2,692.0 2,583.8 2,521.9 2,560.7 2,406.4 2,247.5 2,409.5 2,564.7 2,357.3 2,371.7 2,445.1 2,659.2 2,583.5 2,580.2 2,590.7 2,181.9 2,636.6 2,488.8 2,311.4 2,459.9 2,521.4 2,569.0 2,586.7 2,611.7 2,223.2 2,181.9 2,692.0 2,483.8 129.8

Table 2 Major ion composition of waters collected from springs (Temp in C; EC in lS cm1; concentrations in mg l1)

Spring code

Date

Temp

Environmental Geology (2004) 45:808817

Pm1

Pm2

Pm3

30-Aug-1993 21-Sep-1993 10-Nov-1993 03-Jun-1994 18-Jul-1994 21-Aug-1994 12-Dec-1994 25-Apr-1995 26-May-1995 12-Sep-1995 09-Jan-1996 30-Aug-1993 21-Sep-1993 10-Nov-1993 07-Mar-1994 18-Jul-1994 21-Aug-1994 12-Dec-1994 25-Apr-1995 12-Sep-1995 30-Aug-1993 21-Sep-1993 10-Nov-1993 07-Mar-1994 03-Jun-1994 21-Aug-1994 12-Dec-1994 25-Apr-1995 12-Sep-1995 Minimum Maximum Average Standard dev.

Original article

Fig. 5 Average saturation indices of Pamukkale thermal waters with respect to different minerals

The precipitation of thermogene travertine at the Pamukkale plateau should be regarded as the surface signature of the deep circulation of meteoric waters through marble and limestone formations. At Pamukkale plateau fossil and fresh travertine deposits occupy an area of about 10 km2 (Altunel and Hancock 1993). The real occupied area, however, must be larger since travertine deposits have been drilled in the valley close to the plateau with over 110 m thickness (Ozpinar 1994). 230Th/234U age determinations on fossil travertine samples collected in the Pamukkale area and its surroundings indicate that travertine deposition has been progressing over the last 400,000 years (Altunel and Hancock 1993, 1996). Nevertheless, this age could possibly be higher because the uranium series method is only appropriate for an age range of 5,000 to 400,000 years (Smart 1991). In fact, the study conducted by Engin and Guven (1997) to determine the age of Pamukkale travertine deposits using the Thermoluminescence method, indicated an age of 828,000 years. Engin and others (1999) applying the Electron Spin Resonance method estimated an age for the travertine deposits of 1,110,000 years. Although travertine is not an ideal material for Electron Spin Resonance dating (Grun 1989), Engin and others (1999) suggested that specically collected wellcrystallized crusts could give signicant results. The age estimations probably show that the relative timing of travertine deposition activity at the site started during the late Pleistocene. In fact, a large proportion of the European thermogene travertine deposits also date to the Pleistocene or late Pliocene (Pentecost 1995).

Discussion
Calcite dissolution-precipitation kinetics for travertine age and size in the eld is thought to be essential in constructing this section. Nevertheless, the knowledge on the hydrological circulation of groundwater in the Pamukkale area is also crucial in fullling the purpose of the paper. Hydrological considerations indicate that the water recharging the Pamukkale thermal system is mainly rainfall and rarely melting of the winter snow pack that falls in the interior highlands. Meteoric water, which has

percolated to the local groundwater system at a shallow level in the ground, ows to the thermal system. This ow is driven by the hydraulic gradient through highly permeable faults and fractures. During a deep convection cycle from recharge area to discharge area, the cold groundwater attains heat from the asthenospheric intrusions. Thermal uid at depth in the high-temperature zone is relatively rich in gaseous components originated from the heat source. Based on Eq. (7), the thermodynamic equilibrium constant decreases with increasing temperature, resulting in increasing saturation index. Hence, in the system, under the assumption that no signicant external effects are present (e.g., mixing), the thermal uids should be super-saturated with respect to carbonate minerals at depth. Groundwater ascension is facilitated by the decrease of the water density caused by heating at depth. As the thermal uid ascends towards the surface, the hydrostatic pressure imposed on it decreases, resulting in boiling process, in which gas components (e.g., mainly carbon dioxide and hydrogen sulde) enter the vapor phase. Meanwhile, the thermal uid is mixed with an increasing amount of relatively cool groundwater (calcium-bicarbonate type) at shallow depths because, as the gases are removed from the thermal uid, the decrease in pressure allows the entry of fresh groundwater into the system. The vapor from the boiling zone dissolves or condenses in cool groundwater by oxidation to form bicarbonate waters. The diluted thermal water becomes under-saturated with respect to calcium carbonate due to the cooling process because the solubility of carbon dioxide increases with decreasing liquid temperature, resulting in an increased carbon dioxide partial pressure [Henrys law, see Eq. (8)]. This aggressive environment at depth generates secondary porosity in the soluble rocks. The acidity of the uid determines the fate of the saturation state of carbonate minerals. An increase in acidity of the uid preferentially decreases ion activity product through a decrease in carbonate ions, and due to Eq. (7), saturation index decreases, leading the groundwater to pronounced under-saturation. Pamukkale thermal waters present slightly saturated conditions with respect to calcium carbonate (the minimum saturation values calculated for calcite and aragonite is )0.26 and )0.12, respectively) and high carbon dioxide partial pressure (as much as 1.6 atm). The springs that were sampled do not show a tendency to deposit calcite at the outlet but already have the potential to do so because the calcium concentration is present in signicant amounts (ca. 460 mg l1). When the water ows freely on the surface at the travertine site, the thermal water continues to lose carbon dioxide and thus deposits calcium carbonate. Through the years, the equilibrium state of Pamukkale thermal waters must have been different because the paleo-climate, -hydrology and/or seismic activities prevail upon the quantity of dissolved carbonate in the thermal uid. As previously recognized, hydrothermal circulation at the Pamukkale hydrothermal eld is mainly driven by meteoric water inltration. During wet climate conditions, we 813

Environmental Geology (2004) 45:808817

Original article

would expect the greater availability of meteoric water to provoke the dynamics of the system, promoting high active hydrothermal circulation. So, during wet climate conditions the groundwater is recharged by more precipitation, a preferential increase in pressure occurs in the system, and consequently higher ow rates of thermal water take place at the springs in the discharge area. On the other hand, during dry climate conditions, the recharge by meteoric waters is relatively lower, and the response in hydrothermal circulation could be expressed by lower ow rates at the springs. The origin of the extensional tectonic regime in western Turkey has been mainly devoted to the orogenic collapse model (e.g. Seyitoglu and Scott 1992; Seyitoglu and others 1992), which is based on the idea that extensional tectonism is related to the spreading and thinning of an over thickened crust. This thinning mechanism, which continues, leads to an asthenospheric mantle intrusion that continuously supplies heat and gas to the geothermal systems (Gulec - pers. comm. 2002). This region of Turkey, therefore, has the highest geothermal potential with an average reservoir temperature of 251 C (Gulec and others 2002). It is very difcult to suggest whether the heat and gas contributions from the intrusions have changed through historical periods. Yet, if it could be assumed that magmatic gas emanations have not shown signicant anomalies through the late Quaternary (viz., nearly constant gas contribution), the concentration of carbon dioxide in the thermal uid would be relatively higher during a dry climate as a result of a lower recharge rate. During this climate condition, the lowering of carbon dioxide partial pressure in the boiling zone increases the acidity of the uid. This near-surface reaction leads to super-saturation and the effective self-sealing of vertical permeability proceeds by calcium carbonate precipitation. The wet climate can be described by higher subsurface boiling because the hydrostatic pressure on the light thermal water column is higher and the mixing ratio with cold shallow groundwater increases. Extensive subsurface boiling processes, after carbon dioxide degassing, lowers the temperature of the uid and leads to an increase in calcium carbonate solubility. In this case, the thermal uid becomes under-saturated with respect to calcium carbonate, and calcite deposition takes place at the surface under appropriate conditions. No paleoclimatic study has been performed at Pamukkale so far, but considerable paleoclimatic features can be obtained from the regional geology. Westaway (1993) describes the Neogene sequence in the Denizli Basin as a result of the arid climate. However, during the development of the horst-graben systems, winds prevailed from the west (Aegean Sea) creating a partly humid environment, as indicated by lignite deposits in the Buyuk Menderes graben during the Early-Middle Miocene (Cohen and others 1995), and by lignite beds and bituminous shale in the Gediz graben (Yilmaz and others 2000; see Fig. 1). In the study conducted by Leng and others (2001) some results concerning past climate in the region (back to 10,000 years, almost the beginning of the Holocene) are presented. The study was conducted in Golhisar (3708 N, 814

Fig. 6 The uctuation of climate in Golhisar (after Leng et al. 2001)

2936 E), which is a small mountain lake in Burdur province, at a distance of 90 km to the northeast of Pamukkale. This research is generating a well-dated time series showing the evaporation of lake water and hence how wet or dry the climate was (Fig. 6). Furthermore, the simulation experiments in the project of COHMAP (Cooperative Holocene Mapping Project: a multi-institutional consortium studying late Quaternary environment changes as recorded in geologic data and simulated by numerical models, 1988) reveal that 18,000 years ago, lake levels in the southern part of Turkey (probably including the lakes in the Lake District where Golhisar is located) were high, referring to a humid climate. Generally speaking, it can be concluded that the region has experienced arid climate with partly humid climate interruptions during the Neogene, comprising the Miocene and Pliocene epochs. The climate in the region then has been shifted gradually to humid conditions during the Pleistocene (as evidenced by the travertine). The cycle from wet to dry conditions has continued gradually with some interruptions during the Holocene (see Fig. 6), and nally the area experiences dry climate conditions. Since the lifetime of a thermal system is episodic, changes in the heat ux, self-sealing of pathways and tectonic fractures will modify the hydrology of the system. Important signatures of these processes could be obtained from the travertine deposition at Pamukkale. Past circulation is attested by the existence of travertine deposits around ancient spring emergences. The base level of travertine has not remained static over the late Quaternary because there are fossil travertine formations at altitudes (ca. at 550 m) higher than those of the springs. On the other hand, the existence of a small thermal spring, emerging from travertine formations at the heel of the plateau (see Fig. 2), indicates a deepening of the base level. This base level orientation could preferentially result from calcium carbonate deposition in the subsurface along the ow path (as discussed above) and possibly seismic activities rather than anthropogenic factors. At the

Environmental Geology (2004) 45:808817

Original article

Pamukkale thermal eld, access points to the thermal system such as wells, boreholes and pipes are strictly forbidden. The effect of tectonic activities cannot be neglected because earthquakes may affect the ow rate and physical-chemical features of thermal springs (e.g., Fournier 1989; Bjornsson and others 1990; Bolognesi 2000; Favara and others 2001). Today, at the Pamukkale thermal eld we can observe a decrease in thermal water issue. The ow measurements of thermal springs performed by UKAM during the period 19931998 show a trend of )2.64 l sec)1 in total discharge. In 1981, the mean total ow rate value of Pamukkale thermal springs, calculated by the Electrical Works Research Ofce was about 485 l sec1 (Denizli Governorship and others 1992). The recent measurements performed by UKAM in 1993 and 1998 were about 365 and 255 l sec1, respectively (Fig. 7). This trend in discharge could probably be related to the decreases in regional precipitation. The annual uctuations of precipitation in Denizli Province have been analyzed over the monitoring period of 19571996. Although there are signicant year-to-year variations, the overall trend for the last 40 years suggests a gradual decline in annual precipitation with a trend of )1.24 mm yr1. From a statistical point of view, it must be noted that such a trend would be more visible over a very long time period, at least a hundred years. This decline, however, is still meaningful in indicating a change in the climate in the area. In this case, another important point, which is the residence time of the water in the system, comes to importance because the period of meteorological analysis might be insufcient for a system with a highest residence time. Tritium contents of thermal waters at the outlet and in cold springs at the highest elevation point slightly representing the rainfall are of 3.3 and 17.4 TU, leading to an estimation that the residence time of thermal waters ranges between 25 and 30 years (UKAM 1996). It should be noted that this calculated residence time is a rough estimation because the tritium content in thermal waters represents diluted water. According to Altunel (1994), the rst seismic activity at the Pamukkale plateau occurred 65 years BC, even though Engin and others (1967) and Soysal and others (1981) reported 60 years AD.

Since then, many earthquakes have occurred in neighboring areas, but after the 1984 event with a magnitude of 4.7 (30 km to the east of the Pamukkale area) there is no record of more recent earthquakes (Altunel 1994). In view of these results, the impact of seismic activities on thermal spring signatures should be regarded with some restrictions. As a result of the climatic changes in the region, the recharge area of the Pamukkale hydrothermal system might have extended as high as 12001300 m a.s.l. during the lifetime of the system, with the highest elevation at the Pamukkale catchment border and the distance from the thermal springs being as much as 12 km. The highest recharge area could supply more meteoric water to the system to form huge thermogene travertine accumulations over a wide area. The stable isotopic gradient indicates that Pamukkale thermal waters are fed from meteoric water at altitudes of 750800 m a.s.l. (Fig. 8). The long-term average oxygen-18 concentration of Pamukkale thermal springs is about )9.11 per mil. The altitude estimation is interpreted as the average recharge elevation and it corresponds to the natural topographic situation in the study area. The difference in the altitude of the recharge area from 1300 to 750 m may be due to climatic changes in the region.

Final remarks
Pamukkale thermal waters (35 C) are of calciumbicarbonate-sulfate type and produce travertine deposits over a wide area. The thermal activity at the Pamukkale hydrothermal eld is controlled by a combination of the geomorphology and the permeable geologic structures. Therefore, thermal waters comprise different types of waters that have traveled different distances through the rocks depending on the permeability of each rock type associated with each ow path. The interaction with shallow groundwater at various levels alters the chemistry of thermal uid and promotes super- or under-saturation conditions with respect to calcium carbonate, which later

Fig. 7 Standardized ow rate performed at Pamukkale thermal springs

Fig. 8 d18O and elevation relationship of water samples in the area (data from Ozler 2000)

Environmental Geology (2004) 45:808817

815

Original article

precipitates at depth and/or at the surface. This mechanism is also directly related to the hydrology of the region, depending on the period of travertine accumulation in situ. In fact, the late Quaternary suggests a strong inuence of climatic conditions on the hydrothermal system. More rainfall during wet climate conditions induced more recharge to the system, resulting in high discharge at the springs. In this case, a high-rate of calcium carbonate accumulation would be expected to occur at the surface because thermal uid would be under-saturated with respect to calcium carbonate. In contrast, during the dry climate conditions the calcium carbonate deposition occurs before the thermal uids reach the surface. During this period the recharge feeding the system was relatively lower and the thermal uids would be super-saturated because of the highly acidic environment. Consequently, if we assume that no episodic interruption in the thermal uids discharge rate at the springs has occurred during all climatic conditions, then it could be suggested that calcium carbonate deposition has occurred preferentially at the surface during wet climates and at depth during dry climate conditions. The recent thermal discharge measurements indicate that the total ow rate of the springs is decreasing. The main reason for this trend could be the climatic changes because access to the thermal system in the Pamukkale area by any excavation method is strictly forbidden. It was also determined using meteorological data belonging to almost a halfcentury period that the annual precipitation at Pamukkale hydrothermal eld tends to decrease with time. This climatic change in the area was also detected from geological records. While humid climate conditions prevailed during the late Quaternary, the area has recently been affected by arid climate conditions, followed by some episodic transitions. In the present study, we have identied the response of the Pamukkale hydrothermal system to these climatic changes by using all available data and theoretical concepts to support the results. The results presented here are by no means denitive statements as to what will happen to the rate of the Pamukkale thermal springs in the future, but the study has shown how the system has possibly reacted since antiquity. It would be interesting, in the light of the present ndings, to carry out an investigation on paleohydrology in the region using appropriate tools. Furthermore, future scenarios on hydrothermally inuenced events may be anticipated by constructing numerical simulation models rather than conceptual models.

Altunel E, Hancock PL (1993) Morphology and structural setting of Quaternary travertines at Pamukkale, Turkey. Geol J 28:335 346 Altunel E, Hancock PL (1996) Structural attributes of travertinelled extensional ssures in the Pamukkale plateau, western Turkey. Int Geol Rev 38:768777 Appelo CAJ (1988) Groundwater chemistry. IHE Lecture notes, Delft Bjornsson A, Axelsson G, Flovenz OG (1990) The nature of hot springs in Iceland. Natturufraedingurinn 60:1538 (with English abstract) Bolognesi L (2000) Earthquake-induced variations in the composition of the water in the geothermal reservoir at Vulcano Island, Italy. J Volcanol Geoth Res 99:139150 Capasso G, Inguaggiato S (1998) A simple method for the determination of dissolved gases in natural waters: An application to thermal waters from Vulcano Island. Appl Geochem 13(5):631642 Cohen HA, Dart CJ, Akyuz HS, Barka, AA (1995) Syn-rift sedimentation and structural development of Gediz and Buyuk Menderes grabens, western Turkey. J Geol Soc London 152:629 638 COHMAP Members (1988) Climatic changes of the last 18,000 years: observations and model simulations. Science 241:1043 1052 Denizli Governorship, Ministry of Culture, UNESCO (1992) Pamukkale (Hierapolis) preservation and development plan, and the international workshop on Pamukkale. June 30July 3 1991, Pamukkale, Denizli Dramis F, Materazzi M, Cilla G (1999) Inuence of climatic changes on freshwater travertine deposition: a new hypothesis. Phys Chem Earth (A) 24(10):893897 Drever JI (1997) The geochemistry of natural waters, 3rd edn. Prentice Hall, Englewood Cliffs, New Jersey Dreybrodt W (1988) Processes in karst systems: physics, chemistry and geology. Springer, Berlin Heidelberg New York Engin B, Guven O (1997) Thermoluminescence dating of Denizli travertines from the southwestern part of Turkey. Appl Radiat Isotopes 48(9):12571264 Engin B, Guven O, Koksal F (1999) Electron spin resonance age determination of a travertine sample from the southwestern part of Turkey. Appl Radiat Isotopes 51:68969 Engin K, Guclu U, Uz Z (1967) A catalog of earthquakes for Turkey and surrounding areas (11 AD to 1964 AD). Istanbul Tech Univ, Faculty of Mining Eng, Istanbul Favara R, Grassa F, Inguaggiato S, Valenza M (2001) Hydrogeochemistry and stable isotopes of thermal springs: earthquakerelated chemical changes along Belice Fault (western Sicily). Appl Geochem 16:117 Fournier RO (1989) Geochemistry and dynamics of the Yellowstone national park hydrothermal system. Ann Rev Earth Planet Sci 17:1353 Giggenbach WF (1988) Geothermal solute equilibria. Derivation of Na-K-Mg-Ca geoindicators. Geochim Cosmochim Acta 52:27492765 Grasby SE, Hutcheon I, Krouse HR (2000) The inuence of waterAcknowledgment The authors wish to give special thanks to rock interaction on the chemistry of thermal springs in western Prof. Dr. Nilgun Gulec (Middle East Technical University, Canada. Appl Geochem 15:439454 Geological Department, Ankara-TR) for her helpful comments on Grun R (1989) Electron Spin Resonance (ESR) dating. Quat Int regional tectonism. 1:65109 Gulec N, Hilton DR, Mutlu H (2002) Helium isotope variations in Turkey: relationship to tectonics, volcanism and recent seismic activities. Chem Geol 187:129142 Gunay G, Simsek S, Ekmekci M, Elhatip H, Yesertener C, Dilsiz C, Cetiner Z (1997) Karst hydrogeology and environmental imAltunel E (1994) Active tectonics and the evolution of Quaternary pacts of Pamukkale thermal springs. In: Gunay G, Johnson AI travertines at Pamukkale, Western Turkey. PhD Thesis, (eds) Karst waters and environmental impacts, Balkemia, RotDepartment of Geology, University of Bristol, UK (unpublished) terdam, pp 2935

References

816

Environmental Geology (2004) 45:808817

Original article

Hem JD (1970) Study and interpretation of chemical characteristics of natural waters, 2nd edn. Geological Survey Water, United States Department of the Interior Kehew AE (2001) Applied chemical hydrogeology. Prentice-Hall, Englewood Cliffs, New Jersey Leng M, Eastwood W, Roberts N (2001) Environmental change in the Mediterranean. NERC News, Spring Issue, pp 1011 Mercado A, Billings GU (1975) The kinetics of mineral dissolution in carbonate aquifers as a tool for hydrological investigations, I: Concentration-time relationships. J Hydrol 24:303331 Ozler HM (2000) Hydrogeology and hydrochemistry in the Curuksu (Denizli) hydrothermal eld, western Turkey. Environ Geol 39(10):11691180 Ozpinar Y (1994) Tectonism of Denizli geothermal eld. In: Ozpinar Y (ed) Geothermal Applications Symposium94, Pamukkale University, Denizli, pp 114129 Panichi C, Tongiorgi E (1975) Carbon isotopic composition of CO2 from springs, fumaroles, moffetes and travertines of CentralSouthern Italy: a preliminary prospection method of geothermal area. Proc Second United Nations Symp on the Development and Use of Geothermal Resources, San Francisco, pp 815825 Parkhurst DL, Appelo CAJ (1999) Users guide to PHREEQC (VERSION 2) A computer program for speciation, batchreaction, one-dimensional transport, and inverse geochemical calculations. USGS, Water-Resources Investigations Report 994259 Pentecost A (1995) The Quaternary travertine deposits of Europe and Asia minor. Quat Sci Rev 14:10051028 Seyitoglu G, Scott BC (1992) The age of Buyuk Menderes graben (west Turkey) and its tectonic implications. Geol Mag 129:239242

Seyitoglu G, Scott BC, Rundle CC (1992) Timing of Cenozoic extensional tectonics in west Turkey. J Geol Soc London 149:533553 Smart PL (1991) Uranium series dating. In: Smart PL, Frances PD (eds) Quaternary dating methods, a users guide. Quaternary Research Association, Technical guide 4, pp 4583 Soysal H, Sipahioglu S, Kocak D, Altinok Y (1981) Historical earthquake catalog of Turkey and its environment (2100 BC to 1900 AD). The Scientic and Technical Research Council of Turkey, Ankara Trudgill S (1985) Limestone geomorphology. Longman, Harlow UKAM (1994) Report on conservation and development of Pamukkale travertines, Phase I Final Report. Hacettepe University, Ankara UKAM (1995) Report on conservation and development of Pamukkale travertines, Phase II Final Report. Hacettepe University, Ankara UKAM (1996) Report on conservation and development of Pamukkale travertines, Phase III Final Report. Hacettepe University, Ankara Yilmaz Y, Genc SC, Gurer F, Bozcu M, Yilmaz K, Karacik Z, Altunkaynak S, Elmas A (2000) When did the eastern Anatolian grabens begin to develop? In: Bozkurt E, Winchester JA, Piper JDA (eds) Tectonics and magmatism in Turkey and the surrounding area. Geol Soc London, Spec Publ 173:383384 Westaway R (1993) Neogene evolution of the Denizli region of western Turkey. J Struct Geol 15(1):3753 Vengosh A, Helvaci C, Karamanderesi IH (2002) Geochemical constraints for the origin of thermal waters from western Turkey. Appl Geochem 17:163183

Environmental Geology (2004) 45:808817

817