Hydrogeochemical study of the thermal and mineralized waters of the Banaz (Hamamboğazi) area,western Anatolia,Turkey

The Hamamboğazi spa in western Turkey was built around natural hot springs with discharge temperatures in the range of 30–54°C; the waters have near neutral pH values of 6.50–7.10 and a TDS content between 2,694 and 2,982 mg/l. Thermal water with a temperature of 47.5–73°C has been produced at 325 l/s from five wells since 1994, causing some springs to go dry. A management plan is required in the study area to maximize the benefits of this resource, for which currently proposed direct uses include heating in the district and greenhouses, as well as balneology in new spas in the area. The best use for the water from each spring or well will depend on its temperature, chemistry and location. The thermal waters are mixed Na–Mg–HCO₃–SO₄ fluids that contain a significant amount of CO₂ gas. The chemical geothermometers applied to the Hamamboğazi thermal waters yield a maximum reservoir temperature of 130°C. Isotope results (¹⁸O, ²H, ³H) indicate that the thermal waters have a meteoric origin: rainwater percolates downward along fractures and faults, is heated at depth, and then rises to the surface along fractures and faults that act as a hydrothermal conduit. The basement around the Banaz Hamamboğazi resort is comprised of Paleozoic metamorphic schist and marbles exposed 8 km south and 15 km north of Banaz. Mesozoic marble, limestone and ophiolitic complex are observed a few km west and in the northern part of Banaz. These units were cut at a depth of 350–480 m in boreholes drilled in the area. Overlying lacustrine deposits are composed of fine clastic units that alternate with gypsum, tuff and tuffites of 200–350 m thickness. The marble and limestones form the thermal water aquifer, while lacustrine deposits form the impermeable cap.     

Hydrogeochemical and isotopic composition of a low-temperature geothermal source in northwest Turkey: case study of Kirkgecit geothermal area

Chemical and isotopic compositions of three hot springs and one cold spring in the Kirkgecit geothermal field, located 15 km southwest of Canakkale-Biga in the northwest of Turkey, were monitored five times during 2005 and 2007. The physico-chemical characteristics of the hot springs are average discharge 3–3.5 L/s, surface temperature 45–52°C, pH 8.9–9.3, and electrical conductivity (EC) 620–698 μS/cm. The cold spring has a temperature of 12–13°C, pH 7.5–8.3, and EC 653–675 μS/cm. The hot waters are Na-SO₄ type, whereas the cold water is Ca-HCO₃ type. Chemical geothermometers suggest that the reservoir temperature is around 80–100°C. The isotopic data (oxygen-18, deuterium and tritium) indicate that the thermal waters are formed by local recharge and deep circulation of meteoric waters.     

Hydrogeological investigations of thermal waters in the Sfax Basin (Tunisia)

The Sfax Basin in eastern Tunisia is bounded to the east by the Mediterranean Sea. Thermal waters of the Sfax area have measured temperatures of 23–36°C, and electrical conductivities of 3,200 and 14,980 μS/cm. Most of the thermal waters are characterized as Na–Cl type although there are a few Na–SO₄–Cl waters. They issue from Miocene units which are made up sands and sandstones interbedded with clay. The Quaternary sediments cap the system. The heat source is high geothermal gradient which are determined downhole temperature measurements caused by graben tectonics of the area. The results of mineral equilibrium modeling indicate that the thermal waters of the Sfax Basin are undersaturated with respect to gypsum, anhydrite and fluorite, oversaturated with respect to kaolinite, dolomite, calcite, microcline, quartz, chalcedony, and muscovite. Assessments from various chemical geothermometers, Na–K–Mg ternary and mineral equilibrium diagrams suggest that the reservoir temperature of the Sfax area can reach up to 120°C. According to δ¹⁸O and δ²H values, all thermal and cold groundwater is of meteoric origin.     

Application of selected geothermometers to exploration of low-enthalpy thermal water: the Sudetic Geothermal Region in Poland

The most important intakes of thermal waters within the Sudetic Geothermal Region occur in three separate hydrogeothermal systems: (1) Lądek, (2) Duszniki and (3) Cieplice. All these waters are of meteoric origin and circulate in crystalline rocks to different depths. Their outflow temperatures are between less than 20°C and to about 87°C. To evaluate the geothermal fields in the light of their prospectiveness, to further exploration of thermal energy resources, we took an effort to apply selected isotopic and chemical geothermometers to assess the maximum possible temperatures, which may be found in the reservoirs. The only chemical geothermometers which give a reliable range of reservoir temperatures are SiO₂ (chalcedony), Na–Ka–Ca and partly Na–K ones. The oxygen isotopic geothermometer in the SO₄–H₂O system gives a real range of estimated reservoir temperatures only for deeply circulating waters in the Cieplice area. On the other hand, in the case of CO₂ rich waters in the Duszniki area, where outflow temperatures do not exceed 30°C, application of chemical or isotopic temperature indicators always leads to erroneous results due to the lack of equilibrium in the thermodynamic system of water–rock interaction.     

Geothermometry applications for the Balıkesir thermal waters,Turkey

In this study, reservoir temperatures of Balıkesir geothermal waters in northwestern Turkey are estimated with various geochemical models. The geothermal fluids in the region are represented by Na–SO₄, Na–HCO₃ and Ca–HCO₃ type waters with discharge temperatures up to 98°C. It was determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Balıkesir thermal waters studied by means of Na–K–Mg–Ca diagram, mineral saturation calculations and activity diagrams in the system composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O phases approximate a reservoir temperature of about 120°C. Most of the waters are found to be equilibrated with calcite, chalcedony ± quartz and muscovite at predicted temperature ranges, similar to those calculated from the chemical geothermometers.     

Hydrogeochemistry and geothermometry of thermal springs from the Guelma region,Algeria

This paper reports the results of our studies, the chemical analysis of thermal spring’s waters and their geological settings, the use of different statistical methods to evaluate the origin of the dissolved constituents of spring waters and the estimation of the reservoir temperature of the associated geothermal fields of the Guelma region, Algeria. A major component in 13 spring water samples was analyzed using various techniques. The waters of the thermal springs at Guelma basin vary in temperature between 20 and 94oC. Q-mode hierarchical cluster analysis suggests three groups. The water springs were classified as low, moderate and high salinity. Mineral saturation indices (SI) calculated from major ions indicate the spring waters are supersaturated with the most of the carbonate minerals, and all of the spring water samples are under-saturated with evaporite minerals. The thermal spring waters have a meteoric origin, and all samples are immature with strong mixing between warm and shallow waters, where the temperatures of reservoirs to which the thermal waters are related ranged between 64° and 124°C. The deep circulation of meteoric waters in the study area is supplied by the high geothermal gradient around 4.5°C per 100 m and reaches a high temperature before rising to the surface. The estimated circulation depths ranged from 1425 and 3542 m.     

Hydrogeochemical and isotopic investigation of the Bursa-Oylat thermal waters, Turkey

The Oylat spa is located 80 km southeast of Bursa and 30 km south of Ineg?l in the Marmara region. With temperature of 40°C and discharge of 45 l/s, the Oylat main spring is the most important hot water spring of the area. Southeast of the spa the Forest Management spring has a temperature of 39.4°C and discharge of 2 l/s. The G?z spring 2 km north of the spa, which is used for therapy of eye disease, and cold waters of the Saadet village springs with an acidic character are the further important water sources of the area. EC values of Main spring and Forest Management hot spring (750–780 μS/cm) are lower than those of Saadet and G?z spring waters (2,070–1,280 μS/cm) and ionic abundances are Ca > Na + K > Mg and SO₄ > HCO₃ > Cl. The Oylat and Sızı springs have low Na and K contents but high Ca and HCO₃ concentrations. According to AIH classification, these are Ca–SO₄–HCO₃ waters. Based on the results of δ¹⁸O, ²H and ³H isotope analyses, the thermal waters have a meteoric origin. The meteoric water infiltrates along fractures and faults, gets heated, and then returns to surface through hydrothermal conduits. Oylat waters do not have high reservoir temperatures. They are deep, circulating recharge waters from higher enhanced elevations. δ¹³C_DIC values of the Main spring and Forest Management hot spring are −6.31 and −4.45‰, respectively, indicating that δ¹³C is derived from dissolution of limestones. The neutral pH thermal waters are about +18.7‰ in δ³⁴S while the sulfate in the cold waters is about +17‰ (practically identical to the value for the neutral pH thermal waters). However, the G?z and Saadet springs (acid sulfate waters) have much lower δ³⁴S values (~+4‰).     

The evolution of the hydrothermal IOCG system in the Mantoverde district,northern Chile: new evidence from microthermometry and stable isotope geochemistry

New microthermometric data combined with stable isotope geochemistry and paragenetic relationships support a previously suggested cooling–mixing model for the iron oxide–copper–gold mineralization in the Mantoverde district. Fluid inclusions show characteristics of a CO₂-bearing aqueous NaCl ± CaCl₂ salt system. The evolution of the Mantoverde hydrothermal system is characterized by (1) an early hypersaline, high to moderate temperature fluid; (2) a moderate saline, moderate temperature fluid; and (3) a low saline, moderate to low temperature fluid. Early magnetite formation took place at median temperatures of 435.0°C, whereas hematite formed at median temperatures of 334.4°C. The main sulfide mineralization texturally post-dates the iron oxides and occurred before late-stage calcite, which developed at a median temperature of 244.8°C. Boiling occurs only locally and is of no relevance for the ore formation. The microthermometric and stable isotope data are supportive for a fluid cooling and mixing model, and suggestive for a predominantly magmatic–hydrothermal fluid component during the iron oxide and main sulfide mineralization. Thereafter, the incursion of a nonmagmatic fluid of ultimately meteoric or seawater gains more importance.     

The thermal springs of Aachen/Germany – what Charlemagne didn't know

 The Aachen hot springs flow out from Upper Devonian limestones at the Variscan thrust front of the Rhenish Massif. Hydrogeochemical analyses were used to determine the origin of the water and show that sodium, chloride, and sulfate originate from dissolving evaporites that are influenced by meteoric groundwater. The circulation depths of the Aachen thermal water is estimated to be >3500 m using SiO₂–geothermometry and the regional geothermal gradient of about 30  °C/km. The deep circulation in Paleozoic sandstones, siltstones and shales and a considerable residence time allow rock water reactions which explain the concentrations of Ba, Sr, F and Si. While the thermal water rises into Upper Devonian limestones carbonates are dissolved. Cooler fresh water from the vicinity contributes to the thermal aquifer depending on the pressure head of the springs. Sulfate reduction coupled with methane oxidation can be observed as soon as the water temperature is below 65  °C. Received: 21 September 1998 · Accepted: 19 May 1999     

Hydrogeochemistry,environmental isotopes and the origin of the Hamamayagi-Ladik thermal spring (Samsun,Turkey)

Hamamayagi thermal spring (HTS) is located along the North Anatolian Fault Zone. The thermal spring has a temperature of 36°C, with total dissolved solids ranging from 485.6 to 508.5 mg/L. Hard, brittle, and gray limestones Permian aged are the reservoir rocks of the HTS. δ¹⁸O–δ²H isotope ratios clearly indicate a meteoric origin for the waters. The δ³⁴S value of sulfate in the thermal water is nearly 4.1‰ and implies a diagenetic environment characterized by reduced sulfur compounds. The δ¹³C ratio for dissolved inorganic carbonate in the HTS lies between −1.78 and −1.62‰, showing that it originates from the dissolution of fresh-water carbonates. Quartz geothermometry suggests a reservoir temperature of 52–85°C for the Hamamayagi geothermal field, but chalcedony geothermometers suggest reservoir temperatures between 30 and 53°C.     

Thermal water prospecting results at Jelenia Góra-Cieplice (Sudetes, Poland) versus geothermometric forecasts

 To provide additional volume of thermal water for balneotherapy and space heating the well Cieplice-1 has been deepened from 661 m to 2002.5 m. A spontaneous outflow of water with temperatures reaching 87.8  °C was obtained. Thermal logging revealed 97.7  °C at 1870 m. These results are consistent with earlier estimates based on various chemical geothermometers that indicated water temperatures in the lower parts of the geothermal system possibly exceeding 100  °C. This was also confirmed by the cationic composition geothermometer. The estimates based on the dependence of saturation indices on temperature did not prove correct, suggesting 65  °C as the most probable maximum temperature of the water. Received: 11 Sebtember 1998 · Accepted: 7 January 1999     

Thermal waters of the Hornonitrianska kotlina depression and their utilization

 Slovakia has many areas rich in thermal waters one of which is the Hornonitrianska kotlina depression. At four localities three types of waters are found. The first belongs to the Ca–Mg–HCO₃ type with T.D.S. 0.7 g/l, the second to the Ca–Mg–SO₄ type with T.D.S. 1.37–2.01 g/l and the third to the Ca–Mg–SO₄–HCO₃ type with T.D.S. 0.97 g/l. Discharge at individual localities varies up to 30 l/s and temperatures of water reach 32.5–66.6  °C. The waters are predominantly used for healing, rehabilitation purposes, recreation and heating. Received: 8 March 1999 · Accepted: 7 June 1999     

Isotope–geochemical characterization and geothermometrical modeling of Uttarakhand geothermal field,India

Uttarakhand geothermal area, located in the central belt of the Himalayan geothermal province, is one of the important high temperature geothermal fields in India. In this study, the chemical characteristics of the thermal waters are investigated to identify the main geochemical processes affecting the composition of thermal waters during its ascent toward the surface as well as to determine the subsurface temperature of the feeding reservoir. The thermal waters are mainly Ca–Mg–HCO₃ type with moderate silica and TDS concentrations. Mineral saturation states calculated from PHREEQC geochemical code indicate that thermal waters are supersaturated with respect to calcite, dolomite, aragonite, chalcedony, quartz (SI > 0), and undersaturated with respect to gypsum, anhydrite, and amorphous silica (SI < 0). XRD study of the spring deposit samples fairly corroborates the predicted mineral saturation state of the thermal waters. Stable isotopes (δ¹⁸O, δ²H) data confirm the meteoric origin of the thermal waters with no oxygen-18 shift. The mixing phenomenon between thermal water with shallow ground water is substantiated using tritium (³H) and chemical data. The extent of dilution is quantified using tritium content of thermal springs and non-thermal waters. Classical geothermometers, mixing model, and multicomponent fluid geothermometry modeling (GeoT) have been applied to estimate the subsurface reservoir temperature. Among different classical geothermometers, only quartz geothermometer provide somewhat reliable estimation (96–140 °C) of the reservoir temperature. GeoT modeling results suggest that thermal waters have attained simultaneous equilibrium with respect to minerals like calcite, quartz, chalcedony, brucite, tridymite, cristobalite, talc, at the temperature 130 ± 5 °C which is in good agreement with the result obtained from the mixing model.     

Geothermal energy potential of Tulsishyam thermal springs of Gujarat,India

Tulsishyam thermal springs are located in the Saurashtra region of Gujarat, India with discharge temperatures varying from 39 to 42 °C. The pH of these thermal springs varies from 7.1 to 7.4, indicating neutral character. Though these thermal springs propagate through the near surface layer of Deccan basalt, detailed geochemical analysis of the thermal waters using Piper diagram suggests that the water is interacting with the granitic basement rock. Silica and cation geothermometry estimates have reservoir temperature in the range of 138 to 207 °C categorizing it into a low to moderate enthalpy geothermal system. Furthermore, the area has high heat flow values of 53–90 mW/m² because of shallow Moho depth. The prevailing conditions suggest that the geothermal energy can potentially be exploited through an enhanced geothermal system (EGS). The study also indicates different mineral phases that may precipitate out of water during exploitation of geothermal energy and it should be taken into account while designing an EGS for the area.     

Hornblende–garnet–plagioclase thermobarometry: a natural assemblage calibration of the thermodynamics of hornblende

Calibrations are presented for an independent set of four equilibria between end-members of garnet, hornblende, plagioclase and quartz. Thermodynamic data from a large internally-consistent thermodynamic dataset are used to determine the ΔG° of the equilibria. Then, with the known mixing properties of garnet and plagioclase, the non-ideal mixing in amphibole is derived from a set of 74 natural garnet–amphibole–plagioclase–quartz assemblages crystallised in the range 4–13 kbar and 500–800 °C. The advantage of using known thermodynamic data to calculate ΔG° is that correlated variations of composition with temperature and pressure are not manifested in fictive derived entropies and volumes, but are accounted for with non-ideal mixing terms. The amphibole is modelled using a set of ten independent end-members whose mixing parameters are in good agreement with the small amount of data available in the literature. The equilibria used to calibrate the amphibole non-ideal mixing reproduce pressures and temperatures with average absolute deviations of 1.1 kbar and 35 °C using an average pressure–temperature approach, and 0.8 kbar with an average pressure approach. The mixing data provide not only a basis for thermobarometry involving additional phases, but also for calculation of phase diagrams in complex amphibole-bearing systems. Received: 8 November 1999 / Accepted: 7 July 2000     

Factors controlling copper solubility and chalcopyrite deposition in the Sungun porphyry copper deposit, Iran

The Sungun porphyry copper deposit is hosted in a Diorite/granodioritic to quartz-monzonitic stock that intruded Eocene volcanosedimentary and Cretaceous carbonate rocks. Copper mineralization is associated mainly with potassic alteration and to a lesser extent with sericitic alteration. Based on previously published fluid inclusion and isotopic data by Hezarkhani and Williams-Jones most of the copper is interpreted to have deposited during the waning stages of orthomagmatic hydrothermal activity at temperatures of 400 to 300 °C. These data also indicate that the hydrothermal system involved meteoric waters, and boiled extensively. In this work, thermodynamic data are used to delineate the stability fields of alteration and ore assemblages as a function of fS₂, fO₂ and pH. The solubility of chalcopyrite was evaluated in this range of conditions using recently published experimental data. During early potassic alteration (>450 °C), Copper solubility is calculated to have been >50 000 ppm, whereas the copper content of the initial fluid responsible for ore deposition is estimated, from fluid inclusion data, to have been 1200–3800 ppm. This indicates that initially the fluid was highly undersaturated with respect to chalcopyrite, which agrees with the observation that veins formed at T > 400 °C contain molybdenite but rarely chalcopyrite. Copper solubility drops rapidly with decreasing temperature, and at 400 °C is approximately 1000 ppm, within the range estimated from fluid inclusion data, whereas at 350 °C it is only 25 ppm. These calculations are consistent with observations that the bulk of the chalcopyrite deposited at Sungun is hosted by veins formed at temperatures of 360 ± 60 °C. Other factors that, in principle, may reduce chalcopyrite solubility are increases in pH, and decreases in fO₂ and aCl⁻. Our analysis shows, however, that most of the change in pH occurred at high temperature when chalcopyrite was grossly undersaturated in the fluid, and that the direction of change in fO₂ increased chalcopyrite solubility. We propose that the Sungun deposit formed mainly in response to the sharp temperature decrease that accompanied boiling, and partly as a result of the additional heat loss and decrease in aCl⁻, which occurred as a result of mixing of acidic Cu-bearing magmatic waters with cooler meteoric waters of lower salinity. Received: 8 July 1998 / Accepted: 8 April 1999     

Stability of phlogopite in granitic melts, an experimental investigation

Water-saturated and water-undersaturated experiments (a _{H2 O} = 1.0 and 0.5) were performed in the temperature range 780–1040°C at 2 and 5 kbar in order to determine the upper thermal stability of phlogopite in granitic melts. Starting compositions were: (A) subaluminous mixtures of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous haplogranitic glass; (B) peraluminous mixtures (normative corundum  = 4 %) of 20 wt % synthetic phlogopite and 80 wt % synthetic anhydrous peraluminous haplogranitic glass. The molar quartz: albite: orthoclase ratio of the glasses of the 2␣kbar runs was 35:39:26 and that of the 5 kbar runs 30:42:28. In the subaluminous system, phlogopite is stable up to 820°C at a _{H2 O} = 1.0 and up to 780°C at a _{H2 O} = 0.5. At higher temperatures, it is replaced by enstatite. In the peraluminous system phlogopite has a remarkably higher thermal stability (up to 1000°C at 5 kbar and a _{H2 O} = 1.0) and there is a temperature interval of 80°C at a _{H2 O} = 1.0, and 90–100°C at a _{H2 O} = 0.5 between the first appearance of enstatite and the disappearance of phlogopite. In the peraluminous system, phlogopite is a solid solution (ss) of phlogopite, muscovite, talc and eastonite components. The crystalline product of the phlogopite_ss breakdown reaction is an aluminous enstatite. The MgO-content of the melt depends on the normative corundum content of the starting material and the run temperature. It is independent of pressure. In the subaluminous system, the MgO-content ranges between 0.05 and 0.3 wt % in the temperature interval 780–880°C at both investigated water activities. The MgO-content of the peraluminous melts at a _{H2 O} = 1.0 ranges between 0.4 and 1.7 wt % and at a _{H2 O} = 0.5 between 0.2 and 1.4 wt % in the temperature range 780–980°C. Received: 28 August 1995 / Accepted: 6 August 1996     

Supercooled diopside melt: confirmation of temperature-dependent expansivity using container-based dilatometry

The expansivity of supercooled diopside liquid has been determined using techniques of container-based dilatometry. Two thermal strategies have been employed, one in which the sample is brought to volumetric equilibrium by long-duration dwells at low temperatures (817 °C) and one in which scanning dilatometry of the sample has been performed at somewhat higher temperatures (890–913 °C). The results of both experiments yield a supercooled liquid expansivity for diopside liquid in the temperature range of 817–913 °C of 84.4 ± 2.8 × 10⁻⁴ cm³/mol K. The expansivity is 65% higher than that obtained for diopside melt obtained at superliquidus temperatures using the double bob Archimedean method. Combined fitting of the new low temperature, volume–temperature data from the present study and the superliquidus data from the literature has been performed. The combined fit yields the following equations for the volume–temperature relationship of diopside liquid (T=temperature in °C):

Hydrogeochemical and hydrogeological investigations of thermal waters in the Usak Area (Turkey)

Thermal waters of the Usak area have temperatures ranging from 33 to 63°C and different chemical compositions. These waters hosted by the Menderes Metamorphic rocks emerge along fault lineaments from two geothermal reservoirs in the area. The first reservoir consists of gneiss, schists, and marbles of the Menderes Metamorphic rocks. The recorded reservoir is Pliocene lacustrine limestone. Hydrogeochemical studies indicate that thermal waters were mixed with surface waters before and/or after heating at depth. The results of mineral equilibrium modeling indicate that all the thermal waters are undersaturated at discharge temperatures for gypsum, anhydrite, and magnesite minerals. Calcite, dolomite, aragonite, quartz, and chalcedony minerals are oversaturated in all of the thermal waters. Water from the reservoir temperatures of the Usak area can reach upto120°C. According to δ¹⁸O and δ²H values, all thermal and cold groundwater are of meteoric origin.     

Hydrogeochemical investigations of thermal waters in the northeastern part of Morocco

Northeastern Morocco is characterised by a large number of surface geothermal manifestations. Thermal waters are hosted within sedimentary rocks, and in particular the Liassic dolomitic limestones act as a reservoir. The presence of geothermal waters is closely related to important fault systems. Meteoric water infiltrates along those fractures and faults, gets heated, and then returns to the surface through hydrothermal conduits. Most of the thermal waters are of Na–Cl and Ca–Mg–HCO₃ types. In this paper different geochemical approaches were applied to infer the reservoir temperature. Na–K–Mg^1/2 ternary diagram points to temperatures ranging from 100 to 180 °C. Cation geothermometers suggest an average reservoir temperature of about 100 °C. Mineral solution equilibria analysis yields temperatures ranging from 50 to 185 °C. The silica enthalpy mixture model gives an average value (about 110 °C) higher than that inferred from cation geothermometers.