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Contribution to the study of Greek thermal springs: hydrogeological and hydrochemical characteristics and origin of thermal waters

Nicolaos Lambrakis George Kallergis

Abstract A large number of chemical analyses of Greek thermal waters were evaluated in order to investigate spring water origin, waterrock interaction mechanisms, and estimate the thermal potential of the geothermal areas. Four water types were distinguished from geochemical diagrams. The relatively fresher waters include samples of CaHCO3 and MgHCO3 type waters originating from the schistose Rhodope Massif and the Quaternary basin of Aridea, respectively. Samples of the NaHCO3 water type are typical of springs located in the post-orogenic basins of northern Greece. These hot, deep-rising NaHCO3 waters circulate in a CO2-rich environment that favours the solubility of alkaline ions such as Na from siliceous rocks. Most of the samples belong to the NaCl water type and originate from Greek islands and coastal springs. These are characterized by the mixing of deep thermal solutions with seawater and fresh water. The presence of CO2 in thermal and mineral springs is due to the metamorphism of buried marine carbonate horizons while H2S is due to both local pyrite oxidation and the reduction of sulphates. The use of geothermometers suggested that the investigated geothermal areas have low enthalpy fluids at depth, while higher temperatures are likely present in Milos, Lesvos, Nisyros islands and Xanthi Basin. Rsum Un grand nombre danalyses chimiques des eaux thermales grecques ont t menes de manire investiguer lorigine des eaux des sources thermales, les mcanismes dinteraction avec les roches traverses, et destimer le potentiel des zones gothermiques. Quatre types deau ont t distingues sur base des diagrammes
Received: 8 March 2003 / Accepted: 17 April 2004 Published online: 28 May 2004  Springer-Verlag 2004 N. Lambrakis ()) G. Kallergis Department of Geology, Section of Applied Geology and Geophysics, Laboratory of Hydrogeology, University of Patras, 26500 Rio-Patras, Greece e-mail: nlambrakis@upatras.gr Tel.: +30-2610-997782 Fax: +30-2610-997782 Hydrogeology Journal (2005) 13:506521

gochimiques. Les eaux les plus fraches correspondent respectivement aux chantillons des eaux calco et magnso carbonates du massif schisteux de Rhodope et du bassin quaternaire dAridea. Les chantillons deaux sodi carbonates proviennent typiquement des sources localises dans les bassins posts-orogniques du Nord de la Grce. Ces chaudes et trs profondes eaux sodi carbonates circulent dans des environnements riches en CO2 qui favorisent la solubilit des ions alcalins, tel que le sodium, des roches siliceuses. La plus part des chantillons ont un facies chlorur sodique et proviennent des les grecques ou des environnement ctier. Ces eaux sont caractrises par des mlanges entre eaux profondes avec des eaux de mer et des eaux de surface. La prsence de CO2 dans les eaux de sources thermales et minrales est due au mtamorphisme des horizons de calcaires marins et couverts, tandis que la prsence de H2S est due loxydation locale de la pyrite et la rduction des sulfates. Lutilisation de gothermomtres suggre que les zones gothermiques tudies contiennent des eaux faible enthalpie en profondeur, bien que des tempratures assez leves soient rencontres Milos, Lesvos, sur les les Nisyros et dans le bassin de Xanthi. Resumen Se ha evaluado un gran nmero de anlisis qumicos de aguas termales griegas con objeto de investigar el origen del agua en los manantiales, los mecanismos de interaccin agua-roca, y estimar el potencial termal de las reas geotrmicas. Se distinguieron cuatro tipos de aguas a partir de diagramas geoqumicos. Las aguas relativamente frescas incluyen muestras de agua tipo CaHCO3 y MgHCO3 que se originan en los esquistos del Macizo Rhodope y la cuenca Cuaternaria de Aridea, respectivamente. Las muestras de agua tipo NaHCO3 son tpicas de manantiales localizados en las cuencas post-orognicas del norte de Grecia. Estas aguas calientes y profundas, de tipo NaHCO3, circulan en un ambiente rico en CO2 que favorece la solubilidad de iones alcalinos, tal como Na proveniente de rocas silcicas. La mayora de las muestras pertenecen al tipo de agua NaCl y se originan en islas y manantiales costeros griegos. Estas aguas se caracterizan por la mezcla de soluciones termales profundas con agua de mar y agua dulce. La presencia de CO2 en manantiales termales y minerales se debe a el metamorfismo de horizontes carbonatados marinos enterrados mientras que el H2S se debe a oxidacin
DOI 10.1007/s10040-004-0349-x

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local de pirita y reduccin de sulfatos. El uso de geotermmetros sugiere que las reas termales investigadas tienen fluidos de baja entalpa a profundidad, mientras que las temperaturas ms elevadas es probable que se presenten en Milos, Lesvos, islas de Nisyros y la cuenca Xanthi. Keywords Thermal springs Chemical and isotopic composition Geothermometry Greece

Introduction
There are many thermal springs in Greece due to the geology of the country. Magmatic and volcanic processes, the high mountain chains and active fault systems favour the rise of deep waters that discharge at the surface as thermal springs. The origin of the fluid movement results from a thermal gradient closely relating to volcanic activity, leading to convection. Although numerous studies on the origin and quality of thermal waters in territories in Greece have been made during the last 30 years, none of them concentrates on the entire country. A large number of chemical analyses of thermal waters exist in many technical reports and papers. Their evaluation for the whole of Greece is not an easy task because (1) the origin of the sampling points are not always exactly positioned, (2) the analyses originated from many different laboratories and their accuracy is not evident, and (3) the analyses were made over very different time periods. From 19851988, the Institute of Geological and Mineral Exploration in Greece (IGME) performed a great number of chemical analyses on all known Greek thermal springs (Gioni-Stavropoulou 1983; Orfanos 1985; Sfetsos 1988). About 1,300 analyses were evaluated and the most representative were chosen for each thermal field (Table 1). Chemical patterns of thermal fields resulting from these analyses are in agreement with those given in studies on any particular field and therefore are considered to accurately reflect the mean chemical composition of thermal waters. Similarly, the collected data on isotopic analyses are almost the same during different periods. For example, stable isotope values of spring 76Le (see Table 2) do not vary significantly in time despite being recorded over a 10-year period. The aim of this paper is to describe the main hydrogeological and hydrochemical characteristics of geothermal fields and investigate the origin of thermal waters. Processing of chemical analyses was made using the Phreeqc program. Saturation indexes were also simulated and to estimate the thermal water reservoir temperature all possible geothermometers were applied.

trys heat flow contour lines (in mW/cm ; Fytikas and Kolios 1979). By comparing these maps, it can be easily seen that most thermal springs are mainly located in areas with greater heat flow which originated from intense volcanic activity that took place in recent geological times. Areas with anomalous geothermal gradients are (1) the slow-moving Tertiary tectonic area of the northern Aegean area (Salonica, Migdonia, Anthemus, Strimonas, Drama, Xanthi-Komotini, and Alexandroupolis Basins, the volcanoes of Samothrace, Limnos, Ag. Efstratios and Lesvos Islands) (2) the volcanic arc of the southern Aegean areas, which is bordered by the volcanic centres of Microthiba, Achilion, Lichades, Loutraki, Aigina, Methana, Paros, Thira, Nisiros, Ko and others, and, (3) the Sperchios depression which is not related with obvious volcanic activity. To the west of the described regions, the number of mineral and thermal springs is small. Their presence is always related to that of fault systems.

General Hydrogeological Aspects of the Main Thermal Fields of Greece


Intense volcanic activity in Greece is known from the presence of volcanic rocks found in all isopic zones of continental Greece and the islands. From Tertiary times, the Aegean area has been dominated by orogenic volcanism due to the relative advance of the African plate into the Eurasian mass. Geochronological and geological data show that volcanic activity has migrated southwards with time (Fytikas et al. 1984). This volcanic activity is closely related to fault systems that favour the displacement in depth of ground waters and the development of thermal springs. According to Fytikas et al. (1984) and Pe-Piper and Piper (1989), volcanic activity in the Aegean Sea commenced in the Oligocene and continues to the present day. Two major phases took place. The first stage was the OligoceneMiocene volcanic phase during which the volcanic activity occurred in an East to West orientated zone from Thrace to the Central Aegean. This activity is located in many places of the Central Aegean region (Lichades of Euboea Island, Tinos, Sikinos, Samos and Patmos islands). Petrographically, two rock types are mainly observed: the calcareous alkaline type with the dominance of acid members (andesites and dacites) developed mainly in Thrace, and the sosonitic type. The second stage was the Pleistocene to the Quaternary phase during which the volcanic centres were arranged into the volcanic arc of the south Aegean. Petrographically, the calcareous alkaline series is present with all its members from basalt to ryolithes. Intermediate phases of local volcanic activity also took place from the Miocene to the Quaternary periods. Numerous thermal fields are located in the Tertiary basins of northern Greece. During the Tertiary period when volcanic activity took place, the Rhodope mass (N Greece) shared a long fault of NESW, ENEWSW and NWSE direction that was active throughout the Neogene
DOI 10.1007/s10040-004-0349-x

Geographical Distribution of Mineral and Thermal Springs


Figure 1a shows the geographical distribution of the main thermal springs of Greece, and Fig. 1b shows the counHydrogeology Journal (2005) 13:506521

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Table 1 Chemical analyses of thermal and mineral waters of Greece (Gioni-Stavropoulou 1983; Orfanos 1985; Sfetsos 1988). Calculated temperatures using the Na/K geothermometers, after Fournier 1979 and Truesdell 1975
T C 49.50 28.00 52.50 43.00 52.00 52.00 53.00 43.50 55.00 30.00 39.50 40.50 41.00 52.00 52.00 51.00 44.00 27.00 40.50 40.50 44.50 37.00 50.50 37.10 50.20 35.00 40.80 39.80 36.50 36.20 9.60 9.60 526 526 7.50 491 7.25 488 8.15 630 33.00 29.00 32.00 59.00 61.00 7.85 7,36 43.00 7.20 647 45.00 53.00 7.20 1,017 26.00 146.00 6.90 1,100 80.00 194.00 6.70 1,154 28.00 310.00 0.00 0.00 0.00 0.33 11.76 3.68 0.33 0.50 14.78 16.12 7.85 239 13.00 7.90 259 16.00 0.00 0.44 0.38 1.70 2.16 1.92 0.70 0.19 0.24 1.72 1.76 0.07 0.04 6.60 1,974 21.00 693.00 0.00 9.20 6.80 2,216 31.00 603.00 0.00 9.20 6.59 5.50 2.15 2.15 6.83 6.40 6.96 0.87 1.00 0.76 3.24 3.24 0.20 0.16 7.20 1,891 33.00 288.00 0.00 9.80 6.20 7.00 1,968 28.00 350.00 0.00 9.80 6.00 6.55 3,316 41.00 342.00 0.00 1.60 7.79 42.51 25.21 25.01 24.56 18.75 2.72 2.48 10.00 10.70 10.45 13.30 12.10 10.08 5.28 5.25 7.68 7.72 6.50 3,242 13.00 984.00 2.85 1.48 13.20 26.36 6.20 2,916 16.00 700.00 2.60 1.30 13.20 26.21 2.01 2.20 3.00 2.00 1.80 2.3 0.10 0.10 0.08 1.34 1.24 1.20 0.44 0.22 0.11 0.17 0.17 0.06 0.06 6.30 2,830 16.00 671.00 3.02 1.50 12.79 25.01 2.00 7.40 259 16.00 0.00 1.16 3.27 0.44 0.03 6.85 1,041 115.00 162.00 0.00 0.56 4.07 16.50 1.20 18.29 4.09 18.53 19.07 19.31 13.77 35.19 35.39 35.51 27.99 2.99 2.91 14.61 15.37 14.79 10.83 5.39 3.71 5.71 5.69 0.55 0.69 6.90 1,074 120.00 204.00 0.00 0.48 3.83 17.00 0.80 17.73 6.55 957 295.00 0.00 0.64 7.11 6.70 0.60 10.73 6.65 914 250.00 0.00 0.68 7.11 6.72 0.60 10.83 1.30 1.30 2.10 2.00 0.30 21.20 21.75 22.50 36.75 4.75 4.25 4.50 3.5 0.40 0.20 1.40 1.40 1.60 1.50 1.20 0.75 0.66 0.68 6.70 6.60 6.65 869 198.00 0.00 0.60 7.20 6.75 0.70 10.89 1.30 6.80 4,093 293.00 0.00 1.71 6.90 64.72 4.20 25.89 46.25 5.05 3.13 3.06 3.10 2.30 2.20 0.47 1.77 1.68 1.65 4.38 2.85 2.84 2.78 2.11 2.04 1.94 3.96 3.91 3.98 3.06 6.86 6.51 4.05 3.93 0.65 0.66 6.85 4,157 373.00 0.00 1.90 6.40 65.52 3.80 26.15 46.25 4.97 8.15 314 0.00 0.12 0.48 5.45 0.07 1.77 2.80 1.57 114 216 226 271 256 256 199 236 230 245 241 249 233 244 235 260 72 180 171 299 283 282 133 134 105 170 171 89 89 7.10 8,340 0.00 1.00 27.00 108.0 3.50 3.83 125.28 10.25 67 186 199 258 238 238 165 212 204 224 218 229 208 223 211 244 22 142 131 298 275 273 172 89 58 131 131 40 40 PH TDS (mg/L) SiO2 (mg/L) CO2 (mg/L) H2S (mg/L) Mg2+ (mg/L) Na/K F 79 C Ca2+ (mg/L) Na+ (meq/L) K+ (meq/L) HCO3 (meq/L) Cl (meq/L) SO42 (meq/L) Na/K Tr 76 C

Spring designations

Lithology

1A-Th1

2A-Th2

3X-Th3

4X-Th5

5R-Th6

6R-Th7

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7R-Th8

8R-M1

9R-M2

10D-M7

11S-M8

12S-M9

13S-M10

14S-M11

15S-M14

16S-M15

17S-M16

18S-M17

19S-M18

20S-M19

21S-M21

22S-M22

23S-M23

24S-M25

25M-M44

26M-M45

27M-M46

28M-M47

29Ai-M48

DOI 10.1007/s10040-004-0349-x

30Ai-M49

Lavas and neogene formations Molasses, lavas, quaternary deposits Gneisses, granites, quaternary deposits Gneisses, granites, quaternary deposits Gneisses, amphibolites, travertines Gneisses, amphibolites, travertines Gneisses, amphibolites, travertines Volcanics, granites, travertines Volcanics, ganites, travertines Marbles, granites, quaternary deposits Marbles, granites, quaternary deposits Marbles, granites, quaternary deposits Marbles, granites, quaternary deposits Marbles, granites, quaternary deposits Peridotites, neogene formations Peridotites, neogene formations Peridotites, neogene formations Peridotites, neogene formations Marbles, schists, quaternary deposits Marbles, schists, quaternary deposits Marbles, granites, neogene formations Marbles, granites, neogene formations Marbles, granites, neogene formations Marbles, granites, neogene formations Granites, pleistocene deposits Probably granites, pleistocene deposits Probably granites, pleistocene deposits Probably granites, pleistocene deposits Peridotites and gabbro, neogene formations Peridotites and gabbro, neogene formations

Table 1 (continued)
T C 27.00 21.00 21.80 39.20 25.5 23.50 36.50 37.20 24.0 52.0 38.0 22.0 50.0 27.0 26.0 40.6 24.4 47.0 55.0 48.50 32.00 34.50 7.00 7.10 7.80 7.00 7.15 6.80 6.90 6.60 6.20 6.5 6.5 6.80 7.05 7.00 7.50 6.70 6.70 7.00 39,764 37,705 11,695 26,871 20,269 40,065 39,964 17.00 12.00 17.00 14.60 25.00 23.00 22.00 2,208 14.50 195.0 90.0 16.0 19.50 19.00 22.00 26.00 17.00 41,241 14,855 24.00 38.50 269.0 258.0 18,153 83.00 57.00 33,144 11.70 39.00 0.0 0.0 1.17 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 957 39,523 18.00 140.0 17.0 42.00 0.0 0.0 4.26 67.63 49.22 38.82 96.05 25.21 6.00 97.65 26.01 60.83 47.22 73.64 72.43 66.83 26.00 57.00 46.00 40.00 42.00 46.50 22.50 37.00 37.00 35.00 35.00 58.00 54.00 47.80 36,434 37,160 37,912 3,900 8,983 29.00 27.00 31.00 32.00 75.00 24.0 26.0 17.00 1.00 12.0 0.0 0.0 0.0 0.0 0.0 98.05 99.45 105.0 12.00 22.41 59.20 49.59 52.79 5.19 10.79 2.79 61.59 74.79 42.79 77.60 32.00 19.59 42.0 15.59 34.00 26.00 65.59 64.40 58.40 6.50 1,594 0.0 3.54 7.33 6.70 8,433 0.0 25.01 14.97 4.05 3,354 152.00 111.0 0.0 3.92 12.72 34.03 96.73 14.48 456.97 474.97 484.97 48.39 114.99 6.09 523.97 419.97 219.98 506.97 175.98 1.06 524.97 151.99 353.98 264.98 527.47 524.95 531.47 6.90 3,821 118.00 174.0 0.0 4.96 13.44 35.39 7.00 28,638 140.00 0.0 17.41 63.49 337.48 57.79 2.80 4.20 2.38 0.58 12.46 11.00 11.50 1.20 2.50 1.80 21.51 21.51 8.50 15.00 5.02 0.05 15.00 4.0 10.00 7.50 15.00 15.00 13.00 6.80 23,399 133.00 105.0 0.0 13.41 55.78 271.98 43.71 6.70 12,752 21.00 117.0 0.0 17.21 28.20 163.19 5.55 6.40 36,880 31.00 303.0 0.0 51.62 74.0 495.97 11.00 6.79 6.29 7.23 4.69 9.29 12.29 16.32 5.43 1.87 1.94 1.67 2.43 3.42 4.57 2.39 3.19 3.72 21.11 15.75 18.63 8.93 3.4 3.56 3.71 1.85 1.99 2.31 6.65 14,560 16.70 790.0 0.0 35.62 19.59 173.49 4.88 8.04 6.50 945 22.00 299.00 0.00 4.00 7.44 1.57 0.15 11.63 0.97 205.4 583.9 191.9 355.9 444.9 41.19 33.99 111.3 16.77 547.92 566.92 589.92 55.24 124.48 7.49 634.91 534.93 285.96 593.92 202.97 1.24 612.42 178.97 416.94 311.95 619.91 614.89 56742 6.60 6.35 6.70 810 1,381 856 24.00 28.00 22.00 299.00 448.00 238.00 0.00 0.00 0.00 2.24 3.48 3.88 6.83 12.96 7.16 0.80 1.94 1.46 0.06 0.12 0.13 8.35 15.51 11.25 0.24 0.70 0.82 1.21 1.99 0.35 0.40 20.33 31.00 14.18 17.90 19.51 5.2 7.63 11.87 2.56 72.28 69.50 60.70 7.31 21.75 1.25 36.28 27.93 19.34 75.76 18.99 6.79 60.72 17.40 39.28 30.61 62.58 61.81 56.21 6.70 6.35 6,302 36,783 29.00 40.00 292.00 719.00 0.00 101.64 12.20 62.85 13.20 53.59 70.03 478.21 1.50 14.00 17.37 18.79 77.5 549. 1.91 40.18 6.10 2,453 95.00 1000.0 0.00 6.80 11.03 9.40 0.50 19.13 7.40 1.17 209 143 164 239 221 255 262 161 146 174 322 330 244 290 152 186 159 148 150 153 144 410 188 205 183 164 162 199 162 157 161 161 162 162 152 6.45 6,438 33.00 840.00 0.00 0.001 23.20 71.91 2.31 27.99 75.0 0.08 170 131 177 100 123 216 193 237 247 120 102 135 330 341 222 285 110 150 118 105 107 110 101 468 152 173 147 124 121 165 129 175 120 120 121 121 169 PH TDS (mg/L) SiO2 (mg/L) CO2 (mg/L) H2S (mg/L) Mg2+ (mg/L) HCO3 (meq/L) Na/K F 79 C SO42 (meq/L) Ca2+ (mg/L) Na+ (meq/L) K+ (meq/L) Cl (meq/L) Na/K Tr 76 C

Spring designations

Lithology

31Ai-M51

32Ai-M53

33Ai-M59 34Ai-M60

35Ar-M61 36Ar-M62 37Ar-M64

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38Ar-M65

39Ag-I2

40Ky-I3

41Ky-I4

42Mi-I12

43Mi-I13

44Mi-I14

45Mi-I15

46Mi-I16

47Mi-I17

48Ki-I18 49Ki-I19 50Ki-I20 51Thi-I21 52Thi-I22

53Ana-I23 54Ni-I26

55Ni-I27

56Ni-I28

57Ko-I29 58Ko-I30

59Ko-I31

60Ka-I34

61Ik-I36 62Ik-I37 63Ik-I38 64Ik-I39

65Ik-I40

DOI 10.1007/s10040-004-0349-x

66Ik-I41

Mesozoic limestones, neogene formations, travertines Mesozoic limestones, neogene formations, travertines Recent deposits Mesozoic limestone, neogene formations Marbles, travertines Marbles, travertines Marbles, mesozoic limestones, flysch Marbles, mesozoic limestones, flysch Limestone, sandstone, schists Schists, marbles, alluvium deposits Schists, marbles, alluvium deposits Rhyolitic lavas, tuffs, alluvium deposits Neogene tuffs, conglomerates, alluviums Neogene tuffs, alluvium Neogene tuffs, pyroclastics, alluviums Neogene tuffs, rhyolitic lavas, alluviums Altered volcanics, mud flows-lahar Tuffs, clays Tuffs Tuffs Crystallized limestones Phyllites, pyroclastics, pumice Marbles, clays Andesitic lava, tuffs and pumice Andesitic lava, tuffs and pumice Andesitic lava, tuffs and pumice Flysch, limestone Schists and limestones, mesozoic limestones Flysch with limestone lenses Limestones and dolomites Gneisses, marbles Gneisses, marbles Gneisses, marbles Gneisses, marbles, schists, conglomerates Gneisses, marbles, schists Gneisses, marbles, schists

509

Table 1 (continued)
T C 54.00 55.00 40.00 40.00 30.00 30.05 43.00 65.00 81.50 37.00 80.00 67.00 39.00 25.00 44.00 27.00 1.23 14.00 39.00 1.80 3.80 5.84 45.70 2.00 20.00 127.80 63.80 572.00 0.33 59.70 0.16 43.20 1.71 60.50 26.00 42.50 23.57 22.93 104.4 19.13 13.81 16.81 15.41 13.21 15.81 16.01 47.63 42.60 1.22 69.23 3.92 37.20 23.52 10.24 17.27 51.20 30.31 21.59 28.20 29.20 16.79 26.59 27.19 51.20 54.20 30.39 56.84 81.03 460.20 164.53 268.44 17.75 349.98 212.48 119.99 104.49 499.97 161.07 109.04 136.06 133.05 80.53 108.04 105.04 312.63 1.23 7.53 16.22 2.34 2.00 0.40 0.35 11.99 13.05 17.92 0.53 10.00 6.25 4.40 4.20 10.00 5.25 3.00 3.50 3.50 2.30 3.20 3.80 9.00 27.00 36.00 47.00 54.50 49.00 32.10 27.50 30.00 28.00 38.00 22.50 32.00 31.40 33.00 32.2 28.20 37.00 40.00 33.00 7.40 6.90 9,138 24,818 7.50 9,228 7.20 6,749 6.90 10,747 7.20 10,969 7.70 8,722 7.30 12,821 6.15 39,670 6.40 9,291 6.30 9,462 6.30 16,954 6.40 27,544 7.40 1,731 7.00 20,484 7.00 12,619 6.50 35,664 6.50 1,539 6.10 382 6.50 6.70 345 24,977 1.48 53.25 1.69 36.17 1.56 330.14 0.23 8.00 5.90 6.70 11,120 1,531 79.00 14.00 9.87 4.11 25.99 5.38 147.06 16.00 4.80 0.69 4.63 4.85 2.70 2.32 1.72 6.88 4.09 6.99 5.99 5.25 16.17 12.32 7.93 18.27 27.47 10.08 7.23 10.27 10.11 8.83 14.19 14.69 15.29 6.30 11,167 66.00 9.79 25.99 147.06 5.39 4.47 6.10 12,111 71.00 10.28 28.39 160.07 5.60 4.81 6.30 11,423 64.00 10.04 26.79 150.06 5.60 4.67 182.01 193.04 178.03 177.02 1.26 1.74 388.06 3.89 19.01 562.09 203.97 339.94 20.69 406.94 244.96 134.98 115.48 577.92 191.03 130.02 162.03 158.03 97.01 129.82 127.02 370.07 6.50 7.00 6.40 311 5,176 12,042 38.60 43.00 10.00 1.23 2.38 7.24 2.19 16.21 40.21 1.65 65.28 150.06 0.17 1.73 5.80 2.98 2.49 1.80 1.35 74.01 192.02 1.04 9.05 9.45 6.12 6.45 5.95 5.70 0.93 0.45 36.99 0.33 1.99 43.41 0.78 1.31 2.05 42.00 27.32 14.70 14.65 56.00 14.26 9.30 11.74 11.65 6.93 8.87 9.08 33.77 6.95 6.90 7.90 26,749 28,696 9,983 17.70 17.00 19.00 20.00 50.00 0.0 0.0 0.0 59.34 54.02 28.64 36.79 45.20 14.12 353.98 379.97 117.87 10.00 10.00 9.05 2.93 2.53 3.01 411.94 442.4 147.88 40.32 44.39 16.90 161 157 241 270 157 183 144 176 180 171 192 311 151 351 144 156 244 228 165 162 164 180 186 139 171 160 155 157 162 164 179 163 6.80 39,828 22.00 25.00 0.0 71.64 64.40 524.97 15.00 2.09 617.42 61.38 162 6.70 39,013 24.00 25.00 0.0 71.63 65.00 514.97 13.00 2.16 604.92 59.68 154 112 121 120 115 218 257 115 147 144 138 142 132 157 314 109 373 100 114 223 202 125 121 124 142 150 95 132 118 113 115 121 124 141 122 PH TDS (mg/L) SiO2 (mg/L) CO2 (mg/L) H2S (mg/L) Mg2+ (mg/L) Na/K F 79 C Na/K Tr 76 C Ca2+ (mg/L) Na+ (meq/L) K+ (meq/L) HCO3 (meq/L) Cl (meq/L) SO42 (meq/L)

510

Spring designations

Lithology

67Ik-I42

68Ik-I43

69Ik-I44 70Ik-I45 71Sa-I46

72Le-I47 73Le-I48 74Le-I49

75Le-I50

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76Le-I51

77Le-I52

78Le-I53 79Le-I54

80Le-I55 81Le-I56

82Le-I57

83Le-I58

84Le-I59

85Sa-I60

86Sa-I61

87Lo-P43

88Me-P45

89Me-P45a

90Me-45b

91Me-P46

92Me-P46a

93Sp-S5

94Sp-S7

95Sp-S8

96Sp-S9

97Sp-S10

98Sp-S12

99Sp-S13

DOI 10.1007/s10040-004-0349-x

100Sp-S14

Gneisses, marbles, schists Gneisses, marbles, schists Gneisses, marbles Gneisses, marbles Gneisses, marbles, recent deposits Lavas Andesitic lavas Andesitic lavas, recent deposits Ignimbrites, recent deposits Ignimbrites, recent deposits Ignimbrites, recent deposits Ignimbrites Marbles, clays and sandstones Lavas, recent deposits Marbles, schists, peridotites Alterated lavas and recent deposits Marbles and schists, basalts, recent deposits Marbles, schists, recent deposits Gabbro, basalts, granites Gabbro, basalts, granites Mesozoic limestones, recent deposits Mesozoic limestones, recent deposits Mesozoic limestones, recent deposits Mesozoic limestones, recent deposits Mesozoic limestones, recent deposits Mesozoic limestones, recent deposits Jurassic limestones, ophiolites, quaternary deposits Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits

Table 1 (continued)
T C 38.00 33.20 32.60 43.50 1342 1620 1044 1340 59.00 11.00 19.3 2.80 7.20 28.00 12.00 3.54 3.04 3.36 33.31 0.17 0.20 9.00 10.90 14.60 7.50 16,00 22.40 24.90 23.10 9.00 12.00 41.00 2.18 32.25 2.72 2.40 4.80 19.32 2,76 0.20 10.00 4.30 1.01 63.50 28.22 5.59 5.52 14.24 8.00 1.68 26.22 3.52 1.92 4.04 2.72 3.55 34.59 6.08 4.00 4.63 5.59 72.20 59.00 73.00 35.80 39.0 28.00 28.00 28.00 29.50 34.50 27.50 32.5 18.00 30.5 28.00 30.00 16.80 20.30 7.15 4,207 7.10 2,039 7.30 1,223 7.40 1,235 8.25 7.40 7.40 7.45 7.70 7.40 374 16,557 1,953 925 615 1,228 6.80 2,110 0.30 0.14 3.50 0.40 0.12 0.12 0.44 9.88 9.70 14.50 55.02 0.43 0.43 0.40 1.30 6.20 6.10 6.15 6.10 6.40 7.00 7.90 34,886 33,847 33,741 30,484 23,076 32,709 1,051 0.0 0.0 0.0 0.0 27.62 26.02 27.22 25.09 50.04 63.65 3.12 65.82 79.20 83.20 72.39 53.20 44.79 6.00 459.20 434.19 435.19 390.54 306.13 443.19 10.80 11.40 11.00 10.60 10.12 7.00 10.00 0.02 8.81 9.93 10.73 8.82 8.57 3.17 8.08 8.73 3.45 3.57 3.14 3.41 11.23 3.49 3.52 3.40 2.56 3.85 6.50 34,061 24.00 50.86 79.24 437.67 11.51 4.49 9.15 325 43.40 6.47 0.18 0.40 4.88 0.03 1.40 6.10 10,514 1850.0 4.20 19.21 41.79 72.03 4.20 36.68 99.51 3.60 524.10 541.10 513.10 521.10 463.57 377.07 506.09 7.00 26.40 1.10 224.04 22.40 9.90 0.20 11.40 11.40 11.30 15.80 60.26 7.00 19,297 39.19 40.04 242.10 6.50 11.57 288.05 26.66 0.08 0.38 51.32 24.28 23.22 23.96 21.80 2.93 48.07 5.70 4.52 2.11 48.29 5.74 2.84 1.44 3.66 3.79 3.66 13.50 5.18 PH TDS (mg/L) SiO2 (mg/L) CO2 (mg/L) H2S (mg/L) Mg2+ (mg/L) Ca2+ (mg/L) Na+ (meq/L) K+ (meq/L) HCO3 (meq/L) Cl (meq/L) SO42 (meq/L) Na/K F 79 C 158 216 78 157 153 154 152 156 147 147 32 96 269 128 136 109 162 196 192 194 161 150 Na/K Tr 76 C 116 187 29 115 110 112 109 114 104 103 47 255 82 91 61 121 165 158 159 118 107

Spring designations

Lithology

101Sp-S15

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1.38 212.09 21.21 10.30 4.20 9.70

102Sp-S18

103Sp-S34

104Eu-S112

105Eu-S113 106E-S114 107Eu-S115 108E-S116 109Eu-S117 110Pw-P4 111Pw-P9

112Pw-P10

113Pw-P11 114Pw-P33 115Pw-P34 116S-S75 117T-T23 118H-H3

119H-H4

120H-H5

121H-H23

122H-H24

Mesozoic limestones, quaternary deposits Mesozoic limestones, quaternary deposits, travertines Argillites and sandstones of flysch Mesozoic limestones, neogene formations Travertines Travertines Travertines Travertines Metamorphic rocks Mesozoic limestones Neogene limestones and sandstones Mesozoic limestones, neogene sandstones Neogene formations Cretaceous limestones Cretaceous limestones Flysch Flysch Paleocene limestones, flysch, alluvium Paleocene limestone, flysch, alluvium Paleocene limestones, flysch, alluviums Mesozoic limestones, recent deposits Mesozoic limestones, recent deposits

Spring designations: the first part comprises the serial number that follows the initials of the spring location. The second part comprises the corresponding Greek water department and the springs serial number taken from the reports of Gioni-Stavropoulou 1983; Orfanos 1985; Sfetsos 1988. Spring locations: A Alexandroupolis Basin, X Xanthi basin, R Mass of Rhodhope, D Dramas basin, S Strymonas basin, M Migdonia basin, Ai Anthemous basin, Ar Aridea basin, F Florina basin, Ag Islands of Agina, Ky Kynthos, Mi Milos, Ki Kimolos, Thi Thira, Ana Anafi, Ni Nisiros, Ko Kos, Ik Ikaria, Le Lesvos, Sa Samothraki, Lo Loutraki Basin, Me Methana Basin, Sp Sperchios Basin, Eu Euboea Island, Pw W. Peloponnesus, T Thessalia, H Epirus. Water Departments: Th Thrace, M Macedonia, I Islands, S Sterea Hellas, P Peloponnesus, T Thessalia, H Epirus

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511

512 Table 2 Isotopic composition of thermal-waters from the main thermal fields of Greece Locations Gennisea (Xanthi Basin) Eleytheres Nigrita (Strimon Basin) Volvi (Migdonia Basin) Lagadas (Migdonia Basin) Kynthos Milos Ikaria Lesvos Springs 3X 11S10 15S10 25M8 25M10 26M8 27M8 40Ky7 43Mi7 42Mi7 64Ik10 76Le1 76Le6 76Le9 74Le9
10

d18O%o 6.24 7.09 8.71 9.5 9.35 9.3 8.4 0.08 +1.5 4.91 1.4 4.94 5.49 5.3 4.7

dD%o 49.06 49.82 62.48 67.3 66.35 67.7 59.6 1.2 +6.5 24.6 10.1 33.1 32.7 38.5 32.9

Locations Lesvos Methana Loutraki Edipsos (Euboea) Kamena Vourla (Sperchios Basin) Thermopyles (Sperchios Basin) Hypati (Sperchios Basin) Kyllini Kaiafas

Springs 84Le 88Me6 89Me5 87Lo5 104Eu3 105Eu3 106Eu3 93Sp2 95Sp 96Sp2 98Sp5 102Sp4 112P10 114P10
9

d18O%o +0.5 4.80 5.69 7.64 0.37 0.00 0.26 4.91 8.40 5.76 7.30 7.90 5.99 2.63

dD%o 0.6 26.1 30.2 44.7 +0.3 0.9 +2.2 27.1 48.6 31.3 55.5 50.5 33.2 11.1

1 4 8

2 3 Papastamataki and Leonis 1982a, 1985 Papastamataki and Leonis 1982b Papastamataki and Leonis 1982c 5 6 7 Papastamataki and Leonis 1982d Anonymous 1984 Barnes et al. 1986 Lohnert 1988 9 10 Poutoukis and Dotsika 1993 Michelot at al. 1993 Mitropoulos and Kita 1997

Fig. 1 Distribution map of the principal thermal waters of Greece

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513 Fig. 2 Classification of the thermal-water springs using the expanded Durov diagram

Fig. 3 Logarithmic plots of relationships between concentration (meq/L) of chloride vs. sodium (a) and calcium (b) in NaHCO3 type Greek thermal waters

period. The area was shaped by strike-slip faulting and related extension processes. Tertiary basins are related and controlled by these faults that are associated with a different basin type and are parallel to the long axes of the basins (Koukouvelas and Aydin 2002). In this way, the Tertiary basins of northern Greece were formed. These faults played a very significant role in allowing the thermal fluids to rise from their storage zones (reservoirs), to regional aquifers (Dimopoulos and Aggelidis 1986; Andronopoulos 1967; Kolios 1985, 1986; Dimopoulos 1989; Traganos 1991). In these aquifers, thermal waters are localized in neogene sediments such as sandstone, calcareous sandstone, and conglomerates with depths of over 200 m (Kolios 1985; Karydakis and Kavouridis 1983; 1989). Deep thermal waters rising in western Peloponnesus, where volcanic manifestations are unknown, are also loHydrogeology Journal (2005) 13:506521

calized in sands and conglomerate intercalations of neogene formations (Kallergis and Lambrakis 1992, 1993). The tectonic formation of west Peloponnesus played a significant role in the appearance of thermal springs. The springs are located on an axis parallel to WNSESE faults (Kiskyras 1962). Thermal waters of the Loutraki-Sousaki area springs belonging to the volcanic Aegean Island arc, which experienced recent volcanic activity, are localized in Pleistocene conglomerates (Schroeder 1985; Fytikas and Kavouridis 1985). The rise of thermal water in the region is related to an active EW trending fault system located in the eastern part of the Golf of Corinth, which was level before the deposition of the neogene sediments in the basin of Corinth (Fytikas and Kavouridis 1985). Apart from the above-mentioned springs, very important thermal fields of Methana and the islands of Milos,
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514

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515

Serifos, Syros, Paros, Thira, Ios, Naxos, Syfnos, Amorgos, Kos, Nisiros and Euboea belong to the volcanic Aegean island arc. Volcanic rocks are very common above a crystalline substratum that characterised all islands of the central Aegean (Durr et al. 1978; Boronkay and Doutsos 1994). During the Pleistocene, extensive andesitic volcanism with different kinds of calcalkaline pyroclastic products and lavas (Fytikas 1977) took place on Lesvos, Milos, Thira and Nisyros. This volcanism, caused by thermal anomalies at relatively shallow depth, is proved by the presence of fumaroles on Milos and Nisyros (Fytikas et al. 1989; Chiodini et al. 1993). Thermal waters rise to the surface either directly from the crystalline substratum and volcanic rocks, or to small alluvial aquifers in Quaternary deposits. Quaternary deposits of the Sperchios Valley, very close to Euboea Island, host the thermal waters of Ypati Spring in conglomerates (Marinos and Frangopoulos 1973), as at Kammena Vourla and Thermopyles (Orfanos and Sfetsos 1975). The valley is delimited by WNWESE oriented faults that relay thermal fields with the sea (Georgalas and Papakis 1966). Thermal waters also rise to the alluvial aquifers in the areas of Aridea (Tzimourtas 1986), Therma of Xanthi, and the volcanic islands of the Aegean Sea.

Classification and Hydrochemical Characteristics of Thermal Springs


The expanded Durov diagram (Fig. 2; Lloyd 1965), which is congener to the Langelier and Ludwig (1942) diagram, is used for a first classification of Greek thermal waters. It is clear from the diagram that the waters can be grouped into four main water types: CaHCO3 type, MgHCO3 type, NaHCO3 type, and the NaCl type. Springs originating directly from crystalline rocks in northern Greece (Aridea internal basin and the Rhodope massif) belong to the first two types of thermal water (CaHCO3 and CaMgHCO3 type waters). These waters have a small concentration of total dissolved solids (TDS; Table 1). After Ellis and Machon (1977) HCO3 waters are considered to occur in volcanic areas where steam containing CO2 condenses into the liquid phase. Giggenbach (1991) indicates that HCO3 waters can also reflect interaction of CO2 charged fluids at lower temperatures as well as mixing with local groundwater. Samples from the post-orogenic basins (Alexandroupolis, Xanthi, Strimonas, Migdonia Basins) belong mainly to the NaHCO3 water type. Their content in TDS is lower than that of the next type of NaCl waters in which Na is considered to be derived from mixing with seawater. The dominance of Na in these springs (see Fig. 3a, where the dotted line is the seawater mixing line) could be caused by the waters increased alteration capacity due to
Fig. 4 Logarithmic plots of relationships between concentration (meq/L) of chemical species a chloride vs. Na/Cl, b chloride vs. bromide, c chloride vs. sulphates d chloride vs. magnesium, e calcium vs. sulphates, f Mg/Ca vs. SO4/Ca, g chloride vs. boron, h chlorides vs. nitrates in NaCl type Greek thermal waters Hydrogeology Journal (2005) 13:506521

the high CO2 concentration that favours the solubility of alkaline elements from silicic rocks (Ellis and Mahon 1977). However, in some cases, ion exchange phenomena between Na and Ca could also be responsible for sodium and calcium concentrations (samples from Alexandroupolis-Xanthi Basin, Sperchios Basin, western Peloponnesus; Fig. 3b). The above-mentioned hydrochemical process is also encountered in other geothermal areas with high CO2 levels as in the inner basin of Rhodope, in Anthemous Basin, in Lesvos Island and in Sperchios Basin. Most of the samples were classified into the NaCl water type and are characterised by high TDS values and a Na/Cl ionic report of about 0.85, very close to that of seawater (for seawater Na/Cl=0.84; Fig. 4a). This water type comprises almost all the samples from island geothermal fields and from coastal springs. Their chemical composition seems to be strongly affected by water of sodium-chloride composition as Minissale et al. (1989; 1997) have also shown. NaCl type waters could be potentially equivalent to seawater mixing with meteoric water or waters having dissolute marine evaporites or deep circulation of recent seawater. Aquilina et al. (2002), demonstrated that in the Balaruc thermal fluids, which are a mixture of karst waters and waters of marine origin, the thermal end-member is itself a mixture of seawater and meteoric palaeowater. Assuming that deep circulation of seawater was the source of the dissolved salts, one would expect the water to have the geochemical characteristics of seawater as suggested by the correlation between Na and Br in the islands (r>98%) (Fig. 4b). Figure 4c exhibits two groups of samples with good correlation between Cl and SO4 (r>98%). Most of the water samples belong to the first group. The concordance between the thermal fluid regression line and the seawaterrainwater mixing line, suggests the same origin of these ions: seawater. However, the small discrepancy between the two lines, especially for the more saline samples, could be attributed to increased amounts of sulphates caused by the dilution of anhydride if brines exist at depth, or to the oxidation of pyrite according to the reaction, FeS2+4.75 O2+1.5 H2O+4e$Fe(OH)3 +2SO42 (Appelo and Postma 1993). Samples from Milos, Nisiros and Euboea Islands belong to the second water group, which presents a lack of SO4 in relation to the first group. Divergences from the seawaterrainwater mixing line suggest modification of the original seawater by waterrock interactions. The depletion of magnesium (Fig. 4d) could be attributed to the ion exchange process at high temperature in several calcium-magnesium silicate minerals (Ellis 1971; Giggenbach 1988) or to the following reactions that, according to Schoeller and Schoeller (1985), could be taking place in crystalline rocks. The first is that magnesium concentrations decrease with temperature, and chlorite is formed from the following reaction:

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516

KAl3 Si3 O10 OH2 7:5Mg2 1:5H4 SiO4 9H2 O $ 1:5MgAl2 Si3 O10 OH8 14H K Laumonite or prenite also are formed. The second reaction is that calcium concentrations should increase with depth as a result of anorthite dilution via the reaction, CaAl2Si2O8+H2O+2H+$Ca+2+Al2Si2O5(OH)4. Hence, seawater brings almost the totality of dissolved Cl, Br and SO4. In order to evaluate whether anhydride is diluted, the correlation line between Ca and SO4 is drawn. In Fig. 4e, several groups of samples could be distinguished. One group, suggesting a Ca/SO4 ratio of 1:1 as in the dilution of anhydrite, comprises samples mainly from Ikaria Island where the above-mentioned mineral does not exist. Other groups suggesting Ca/SO4 ratios of 1.33:1 or 3:1, comprise samples from Sperchios Basin or Euboea and Milos islands respectively. Not having a clear image about these relationships, Fig. 4f with normalized concentrations of SO4 and Mg to Ca, was drawn to differentiate the seawater and evaporate end-members (Aquilina et al. 2002). The regression line (r>98%) for the majority of the samples is almost in concordance with the seawater rainwater mixing-line. A few samples from western Peloponnesus and the Anthemous Basin where anhydrite exists, are in discrepancy with the line towards the anhydrite corner, and suggest that dissolution of this mineral may be responsible for the sulphate enrichment of thermal water. Intensified waterrock interactions are obvious in islands thermal waters for which boron determinations are available. In Fig. 4g, samples from Nisyros, Milos, Lesvos, Kythnos and Euboea Islands with an excess of B relative to Cl could be attributed to intensified waterrock interactions. Additionally, nitrate concentrations that exist in most of the samples (Fig. 4h), indicates the participation of fresh water. It should be noted that in addition to the mixing of thermal with cold, fresh and seawater, cases of fractional magmatic water participation should not be ruled out. For example, while drilling on the island of Thira, thermal and mineral water was located which had a TDS content of 53.223 gr/L (Kavouridis et al. 1982), higher than that of seawater. According to Chiodini et al. (1994), the increased values of TDS may be due to the presence of mantle fluids in Thira Island (Palea and Nea Kameni).

Fig. 5 d18O and d2H composition of thermal and mineral waters of the main geothermal springs in Greece. Hellenic rainfall area after Chiodini et al. (1994)

the meteoric rainfall area. Thermal waters from Komotini-Xanthi, Srimonas, Sperchios Basins and Lesvos Island, show strong meteoric contribution while their position under the meteoric water area could mean mixing with seawater. The above results are in accordance with observation in the previous section where it is mentioned that thermal springs rising close to the sea are strongly affected by seawater that enters the hydrological circuit.

Diluted CO2 and H2S Gases in Thermal and Mineral Waters


From Table 1 it can be seen that many thermal and mineral waters contain increased amounts of dissolved CO2 and H2S gases. Springs with high CO2 concentrations are located in the basins of Strimonas, Aridea, Anthemous and Sperchios. The majority of these springs have CO2 levels varying between 200 to 1,850 mg L1. After Barnes et al. (1986), according to stable d13C in CO2 isotope data, the origin of CO2 in thermal fields of Greece is the result of the thermometamorphism of marine limestones. This process also occurs in other similar geothermal areas (Nuti et al. 1980). Thermal and mineral waters containing H2S are encountered in the basins of Strimonas, Migdonia and Sperchios, the area of Methana, the western Peloponnesus, and Epirus. Hydrogen sulphate (H2S) results from the reduction of sulphate ions under suitable conditions and in the presence of bacteria. It may also derive from the oxidation of pyrite and the anaerobic alteration of
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Isotopic Composition of Thermal and Mineral Waters


Table 2 presents values of the stable isotopes in water (d18O and dD) for the main geothermal fields in Greece. The d18O and dD diagram in Fig. 5 has been drawn using data where Greek rainfall areas have also been drawn according to Chiodini et al. (1994). The position of many thermal waters from Euboea, Kynthos, Milos and Lesvos Islands are very close to mean sea water (SMOW) indicating their purely marine origin. Thermal waters from Sperchios, Migdonia, Loutraki Basins, Methana and West Peloponnesus area are close to
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517

Fig. 6 Frequency diagrams for calcite, dolomite, gypsum, chalcedony and quartz saturation indexes

organic matter. In the western Peloponnesus, H2S is produced from the reduction of sulphates present in the gypsum of Trias (Kallergis and Lambrakis 1992). This could also be the case in the areas of Methana and Sperchios. According to Poutoukis and Dotsika (1993), in the Migdonia Basin, H2S is produced from the reduction of pyrite-derived sulphate, although it is much more likely that CO2 produces a solution that is acid, and pyrite is altered according to the following type of reaction: FeS2 H ! Fe2 H2 S

Geothermometry
As made clear in the previous paragraphs, groundwaters of Greek thermal springs acquire their chemical composition at depth by interacting with silicic rocks bearing alkaline elements and some carbonates (mainly marbles). However, they also interact with shallow aquifers or seawaters. In most cases, except for the islands, these shallow aquifers are located in the neogene sediments.

The degree of waterrock interaction in all samples was determined by calculating the saturation index of the minerals calcite (SIC), dolomite (SId), gypsum (SIg), chalcedony (SICh) and quartz (SIQ) using the Phreeqc program. The above saturation frequency index diagrams show that most Greek thermal waters are over-saturated in calcite and dolomite (Fig. 6). The only negative values are encountered in samples of Lesvos and Milos Islands where the contribution of Ca and Mg bearing minerals is not significant due to the dominating volcanic rocks in the islands. Almost all thermal waters are unsaturated in gypsum while the majority are saturated in quartz and less saturated in chalcedony. Thermal waters unsaturated in chalcedony are encountered in samples from the western Peloponnesus and Epirus, Strimonas Basin and the islands of Nisyros, Ikaria, and Lesvos. Consequently, chemical geothermometers are presented, based on the minerals with the highest grades of saturation. Moreover, as seen from Table 3, several geothermometers lead to unaccepted temperature values. Table 3 and Fig. 7 show statistics from the application of selected geothermometers. Fig. 7 shows that when different geothermometers are applied, the estimated temDOI 10.1007/s10040-004-0349-x

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518 Table 3 Statistical parameters from geothermometer application concerning the estimated temperature of thermal waters. SD standard deviation Minimum SiO2 Am SiO2 CriA2 SiO2 CriB3 SiO2 Chalc4 SiO2 Qz5 Na/K FOUR736 Na/K TR757 Na/K FOUR798 K/Mg GIG839 NaKCa10 NaKCaMg11
1 5 9 1

Maximum 20.0 96.0 47.0 120.0 146.0 505.0 468.0 410.0 85.0 292.0 204.0

Average 43.774 20.86 23.538 38.538 69.86 149.081 154.306 187.427 43.726 169.065 72.862

SD 26.645 31.391 29.059 34.243 32.513 81.664 74.989 59.454 13.684 38.238 46.744

Var% 670.0 167.0 313.0 144.0 114.0 106.0 104.0 92.0 131.0 98.0 92.0

114.0 64.0 100.0 53.0 21.0 30.0 18.0 32.0 26.0 6.0 17.0

2 3 4 Fournier 1977 Fournier 1977 Fournier 1977 Fournier 1973 6 7 8 Fournier and Rowe 1966 Fournier 1973 Truesdell 1975 Fournier 1979 10 11 Giggenbach et al. 1983 Fournier and Truesdell 1973 Fournier and Potter 1979

Fig. 7 Frequency diagrams for the estimated temperatures using the quartz, Na/K, N/Mg, NaKCa and NaKCaMg geothermometers

peratures differ. The mean estimated temperatures for all the thermal springs as calculated by the Na, K and Ca based geothermometers, are similar and vary between 149 and 187 C (Table 3). The geothermometers of Truesdell 1975 and Fournier 1979 (Table 4) provided the closest temperature compared to that measured in wells drilled in Milos Island at 1,0001,400-m depth that is greater than
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300 C (Fytikas 1978). According to Liakopoulos et al. (1991), that temperature is 318 C. This could be taken as evidence that in Milos thermal water, a full equilibrium has been achieved between rocks and water in the storage zone. The geothermometers based on SiO2 and Mg correction show values that differ from previous values. It is known that the NaKCaMg geothermometer can be
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519 Table 4 The maximum estimated temperatures (in paranthesis) using the six selected geothermometers Geothermometers SiO2 Qz Na/K (Fournier 1973) Na/K (Truesdell 1975) Na/K (Fournier 1979) NaKCa (Fournier 1973) NaKCaMg (Fournier and Potter 1979) Springs with higher estimate temperatures (C) 45Mi (146), 42Mi(138), 9R (130), 74Le (123), 32Ai (120) 56Ni (114), 78Le (111), 76Le (106) 53Ana (460), 83Le (390), 43Mi (366), 42Mi (357), 5X (299), 72Le (298), 6,7R (281), 55Ni (225), 54Ni (205) 82Le (373), 43Mi (341), 80Le (314), 21S (298), 45Mi (285), 5X (258), 72Le (257), 17S (244) 82Le (351), 43Mi (330), 42Mi (322), 80Le (311), 21S (299), 45Mi (290), 21S (283), 5X (271), 54Ni (188), 55Ni (205) 43Mi (292), 42Mi (283), 53Ana (270), 45Mi (230), 71Sa (225), 17S (213), 4X (210), 55Ni (209), 54Ni (202) 42Mi (176), 43Mi (176), 5X (160), 12S (149), 13S (153), 7R (152), 6R (149), 11S (149), 8R (136), 14S (130)

used in cases where thermal waters mix with cold fresh waters, which is the case for all neogene and tertiary basins. Saline water contribution, however, greatly reduces the reliability of this geothermometer. The low values obtained by the SiO2 geothermometers could be explained by low silicate contents in the storage zone (metamorphosed carbonates rocks in many cases) and/or by partial equilibration of waterrock due to short contact times. Using the above six geothermometers (Table 4), the areas with the highest estimated temperatures are Milos, Lesvos, and Nisyros Islands, and Xanti geothermal field.

Conclusions
In this paper, the basic hydrogeological and hydrochemical characteristics of the Greek geothermal areas are presented and the origin of thermal and mineral spring waters is investigated. These springs occur mainly in the postorogenic basins of the northern Aegean and the Aegean island arc. Geothermal areas are related to recent volcanic activity and active tectonics. Fluid movement is due to volcanic activity and a thermal gradient leading to convection. This is the case for the majority of springs within areas of Tertiary basins of northern Greece and the Aegean island arc. In western Greece, where volcanic activity does not exist, the thermal gradient is due only to depth. Spring waters in islands and coastal areas are typical of marine solutions and result from the mixing of deep thermal reservoir water and with meteoric water. In continental areas, thermal water rising from deep reservoirs is frequently localized in aquifers of neogene sediments such as conglomerates and sandstones, while in some cases it is mixed with karst surface water. Chemical data combined with isotopic data classified thermal springs into four types of water that originate from marine and non-marine sources. The most important type that belong to marine sources, has a Na/Cl ratio of about 0.85, comprises the spring waters of island and coastal regions, and is of the NaCl type. In some cases (e.g. Euboea and Lesvos Islands), it seems that thermal waters are due to direct seawater infiltration. However, the contribution of mantle fluids should not be excluded at least in the more recent volcanic islands (Chiodini et al. 1994). The other three water types originate from nonHydrogeology Journal (2005) 13:506521

marine sources. The NaHCO3 type occurs in the internal areas of post-orogenic basins (e.g. Strimonas, Migdonia, etc.). High amounts of CO2 contribute to the chemical composition of these waters and favour the solubility of alkaline elements such as Na, from siliciceous rocks. Ion exchange phenomena between Ca of the waters and Na from clay minerals should not be excluded, and contributes to the increase of Na content. The two remaining water types, CaHCO3 and MgHCO3, are considered to be associated with local groundwater. The presence of CO2 in the thermal and mineral waters studied is due to the metamorphism of marine carbonates. The occurrence of H2S in spring waters of the Migdonia Basin is due to the alteration of pyrite, while in the Peloponnesus it is due to the reduction of sulphates originating from dissolved gypsum. Geothermometric analysis is related to mean temperatures between 149 and 187 C. These temperatures are probably due to a normal gradient, given that the depth of the post-orogenic basin of Greece is thought to be greater than 4,000 m. The most promising geothermal fields of Greece are encountered in the Milos, Lesvos, and Nisyros Islands and Xanthi Basin.
Acknowledgments The authors wish to express their gratitude to the Editor and the referees for their careful readings of the manuscripts. Their comments, suggestions, and remarks proved indispensable in helping us improve the style and presentation of this paper.

References
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