Assessment of reservoir temperatures of thermal springs of the northern areas of Pakistan by chemical and isotope geothermometry

Chemical and isotope geothermometers, i.e. the Na–K, K–Mg, quartz and δ¹⁸O(SO₄–H₂O), have been applied to estimate the reservoir temperature of the thermal springs in the northern areas of Pakistan. The chemical types of the thermal waters and the effects of mixing of shallow cold water with the thermal end-members are discussed. These waters are neutral to slightly alkaline and have low dissolved contents. Sodium is the dominant cation in almost all the cases. In terms of anions, the hot waters of Budelas are of the SO₄ type, those of Tatta Pani are of mixed character (SO₄ and HCO₃), and the waters from the remaining areas show HCO₃ domination. An absence of tritium in Tatta Pani and Tato thermal springs indicates that they do not have any contribution of shallow young water. In the case of the Murtazabad springs, the wide range of tritium concentrations, negative correlations with surface temperature and Cl, and positive correlation between Na and Cl show that the shallow cold groundwater is mixing with thermal water in different proportions. For the mixed water of Murtazabad thermal springs, ‘isochemical modelling’ using the Na–K, K–Mg and quartz geothermometers indicates an equilibrium temperature in the range 185–200 °C. The δ¹⁸O(SO₄–H₂O) geothermometer gives relatively low temperatures for three springs, whereas two samples are close to the 185–200 °C temperature interval. The reservoir temperatures of Tatta Pani springs (100–120 °C), determined by Na–K and quartz geothermometers, are in good agreement. The δ¹⁸O(SO₄–H₂O) geothermometer gives a relatively higher range (140–150 °C) for most of the Tatta Pani springs. For Tato spring, the isotope and chemical geothermometers (except for the K–Mg) agree on an equilibrium temperature of about 170 °C. Reservoir temperatures of the remaining minor fields are not conclusive due to the lack of sufficient data.     

Chemical and isotope characteristics of the Chachimbiro geothermal fluids (Ecuador)

The parent geothermal water proposed for the Chachimbiro geothermal area has calculated values of 2250 mg/L Cl and approximately 5 bar P_CO2. It comes from a reservoir having an estimated temperature of 225–235 °C, although temperatures somewhat higher than 260 °C may be present at the roots of the system. The geothermal reservoir at Chachimbiro is recharged mainly by meteoric water (about 92%) and secondarily by arc-type magmatic water. Carbon and sulfur isotope data support a magmatic origin for the C and S species entering the geothermal system from below, consistent with indications provided by He isotopes.The thermal springs of Na–Cl to Na–Cl–HCO₃ type located in the Chachimbiro area originate through dilution of the parent geothermal water and have reached different degrees of re-equilibration with country rocks at lower temperatures.     

Geochemical approach to the Bou Hadjar hydrothermal system (NE Algeria)

The Bou Hadjar low-temperature hydrothermal system is located in northeast Algeria. The four main thermal springs that are the subject of the study emerge ith temperatures between 32 and 60°C from allochthonous formations. The reservoir temperature has been estimated from chemical compositions by utilizing simultaneously the silica, gas and sulfate-water oxygen isotope geothermometers, fluid-mineral equilibrium calculations, and a mixing model. According to these thermometric methods, the most probable subsurface temperature is in the range 75–106°C. The mixing model suggests a temperature of 125°C for the parent water.     

Temperature evaluation of the Bugok geothermal system, South Korea

Using a variety of chemical geothermometers and statistical analysis, we estimate the temperature of a possible deeper geothermal reservoir at Bugok, Southern Korea. Shallow thermal aquifers (down to about 400 m depth) are under exploitation in this area; the temperatures (up to 78 °C) of the produced fluids are the highest found in South Korea. Based on hydrochemical data and occurrence, the groundwaters at Bugok can be classified under three groups: Na-SO₄ thermal groundwaters (CTGW) occurring in the central (about 0.24 km²) part of the area; Ca-HCO₃ cold groundwater (SCGW) found in shallow peripheral parts of the CTGW; the intermediate-type groundwater (STGW). The CTGW type is typical of the Bugok thermal waters; they have the highest discharge temperatures and contain very high concentrations of Na (75.1–101.0 mg/L), K (2.9–6.9 mg/L) and SiO₂ (62.0–84.5 mg/L) and are rich in sulfates.The major ion composition of the CTGW suggests that these waters are in partial equilibrium with rocks at depth. The application of various alkali-ion geothermometers yields temperature estimates in the 88–198 °C range for the thermal reservoir. Multiple-mineral equilibrium calculations indicate a similar but narrower temperature range (from about 100 to 155 °C). These estimates for CTGW are significantly higher than the measured discharge temperatures. Considering the heat losses occurring during the ascent of the waters, one can infer the presence of a deeper (around 1.8 km) thermal reservoir in the Bugok area that could be developed for district heating or other direct applications of geothermal heat.     

The thermal springs of Bockfjorden, Svalbard: II: selected aspects of trace element hydrochemistry

Waters from the Trollkjeldene (Troll springs) and Jotunkjeldene (Jotun springs) thermal springs on northern Svalbard have been analysed by ICP-AES, ICP-MS and IC techniques for a wide range of major and trace elements. Although it is plausible that the thermal waters originate from a deep reservoir in siliceous rocks, it appears that a significant component of their hydrochemical signature is derived from dissolution of higher-level Hecla Hoek marbles. Rare earth elements (REEs) show some degree of enrichment of heavy REEs in the water phase, relative to the marbles and to the travertines that precipitate from the waters. A strong positive Eu anomaly is also observed in the waters, suggesting preferential mobilisation of Eu under reducing conditions. The ratio Nb/Ta is rather well-preserved between the marbles, the waters and the travertines.     

Hot spring activity in the Dakongbeng geothermal area, China

The Dakongbeng geothermal area, whose hot springs reach a temperature of up to 96°C, has been considered one of the potential high-temperature hydrothermal systems in south-west China. The concentration of dominant cations and anions indicates an NaHCO₃ type of thermal water, whose major constituents in decreasing order are: Na>K>Ca>Mg, HCO₃>SiO₂>Cl>SO₄. On the basis of the silica geothermometer, cation geothermometers, gas geothermometer and activity diagram, the reservoir temperature is estimated at about 200°C. All the thermal waters have originated from meteoric water of a higher altitude that circulated as ground water at considerable depth along faults. The stability of their contents of Cl, SiO₂, δD, δ¹⁸O and of the Cl/B, Na/Li ratios suggests that the main heat loss process is through steam loss. The geochemistry of the initial liquid has been estimated by single and continuous steam loss. On the basis of its geologic and geographic setting, the Dakongbeng geothermal area appears to belong to the Himalayan geothermal belt and is thus regarded as an area of interest for further study.     

Hydrogeochemical exploration of geothermal prospects in the Tecuamburro Volcano region, Guatemala

Chemical and isotopic analyses of thermal and nonthermal waters and of gases from springs and fumaroles are used to evaluate the geothermal potential of the Tecuamburro Volcano region, Guatemala. Chemically distinct geothermal surface manifestations generally occur in separate hydrogeologic areas within this 400 km² region: low-pressure fumaroles with temperatures near local boiling occur at 1470 m elevation in a sulfur mine near the summit of Tecuamburro Volcano; non-boiling acid-sulfate hot springs and mud pots are restricted to the Laguna Ixpaco area, about 5 km NNW of the sulfur mine and 350–400 m lower in elevation; steam-heated and thermal-meteoric waters are found on the flanks of Tecuamburro Volcano and several kilometers to the north in the andesitic highland, where the Infernitos fumarole (97°C at 1180 m) is the primary feature; neutral-chloride hot springs discharge along Rio Los Esclavos, principally near Colmenares at 490 m elevation, about 8–10 km SE of Infernitos. Maximum geothermometer temperatures calculated from Colmenares neutral-chloride spring compositions are 180°C, whereas maximum subsurface temperatures based on Laguna Ixpaco gas compositions are 310°C. An exploration core hole drilled to a depth of 808 m about 0.3 km south of Laguna Ixpaco had a bottom-hole temperature of 238°C but did not produce sufficient fluids to confirm or chemically characterize a geothermal reservoir. Hydrogeochemical data combined with regional geologic interpretations indicate that there are probably two hydrothermal-convection systems, which are separated by a major NW-trending structural boundary, the Ixpaco fault. One system with reservoir temperatures near 300°C lies beneath Tecuamburro Volcano and consists of a large vapor zone that feeds steam to the Laguna Ixpaco area, with underlying hot water that flows laterally to feed a small group of warm, chloriderich springs SE of Tecuamburro Volcano. The other system is located beneath the Infernitos area in the andesitic highland and consists of a lower-temperature (150–190°C) reservoir with a large natural discharge that feeds the Colmenares hot springs.     

Hydrology,hydrochemistry and geothermal potential of El Chichón volcano-hydrothermal system,Mexico

Fluid and heat discharge rates of thermal springs of El Chichón volcano were measured using the chloride inventory method. Four of the five known groups of hot springs discharge near-neutral Na–Ca–Cl–SO₄ waters with a similar composition (Cl ∼ 1500–2000 mg kg⁻¹ and Cl/SO₄ ∼ 3) and temperatures in the 50–74 °C range. The other group discharges acidic (pH 2.2–2.7) Na–Cl water of high salinity (>15 g/L). All five groups are located on the volcano slopes, 2–3 km in a straight line from the bottom of the volcano crater. They are in the upper parts of canyons where thermal waters mix with surface meteoric waters and form thermal streams. All these streams flow into the Río Magdalena, which is the only drainage of all thermal waters coming from the volcano. The total Cl and SO₄ discharges measured in the Río Magdalena downstream from its junction with all the thermal streams are very close to the sum of the transported Cl and SO₄ by each of these streams, indicating that the infiltration through the river bed is low. The net discharge rate of hydrothermal Cl measured for all thermal springs is about 468 g s⁻¹, which corresponds to 234 kg s⁻¹ of hot water with Cl = 2000 mg kg⁻¹. Together with earlier calculations of the hydrothermal steam output from the volcano crater, the total natural heat output from El Chichón is estimated to be about 160 MWt. Such a high and concentrated discharge of thermal waters from a hydrothermal system is not common and may indicate the high geothermal potential of the system. For the deep water temperatures in the 200–250 °C range (based on geothermometry), and a mass flow rate of 234 kg s⁻¹, the total heat being discharged by the upflowing hot waters may be 175–210 MWt.     

Hydrogeochemistry and geothermometry of Changal thermal springs,Zagros region,Iran

This study addresses the hydrogeochemistry of thermal springs that emerge from the Asmari limestone in a gorge at Changal Anticline in the vicinity of the Salman-Farsi dam. The Changal thermal springs vary in temperature between 28 and 40 °C. Chemical and isotopic compositions of the thermal waters suggest two distinct hydrogeological systems: a deep, moderate-temperature (∼40 °C) geothermal system recharged by deeply circulating meteoric waters, and a shallow cold aquifer system related to local groundwater. The source geothermal fluid temperature was calculated using different geothermometers and mineral saturation indexes. Based on chemical and isotopic data, it is hypothesized that: (1) mixing occurs between the ascending geothermal water and shallow cold water; (2) the resulting thermal waters reaching surface are a mixture of 80% local, shallow meteoric water and 20% geothermal water; and (3) the circulation depth of the meteoric water is about 1500 m. The thermal reservoir temperature is estimated to be between 70 and 80 °C according to calculations using different geothermometers and computation of saturation indices for different solid phases.     

Hydrogeochemistry and geothermometry of thermal groundwaters from the Birdsville Track Ridge, Great Artesian Basin, South Australia

The hydrogeochemistry of thermal artesian groundwaters flowing from 12 stock bores along the Birdsville Track Ridge in northeast South Australia has been examined. The Na-HCO3-Cl type groundwater composition has provided a basis for the application of chemical geothermometers to estimating aquifer temperatures and has allowed comparisons of various silica and cation geothermometers. Aquifer and bore penetration depth decrease between Birdsville and Marree from 1220 m to 170 m. A corresponding decrease in measured emergence temperature is also observed (94–31 °C). Chalcedony geotemperature estimates ranging from 110 °C to 41 °C between Birdsville and Marree are considered the most accurate of the various geothermometers tested. Log(Q/K) versus T diagrams have also been evaluated to determine likely aquifer mineral assemblages and reservoir temperatures (111–39 °C). The Birdsville Track Ridge acts as a conduit for low salinity groundwater (total dissolved solids range from 640 mg/l at Birdsville to 1900 mg/l at Marree) in the Great Artesian Basin. Old, slowly migrating groundwater from the deeper basins on either side of the ridge is characterised by higher emergence temperature and higher total dissolved solids. This old groundwater is inferred to have mixed with the younger, lower temperature, lower salinity groundwater that is migrating relatively rapidly along the Birdsville Track Ridge axis. Since the various geothermometers provide distinct types of information, evidence for the mixing is provided by the interpretation of the different temperature estimates. Silica equilibration temperatures reflect aquifer temperatures along the ridge axis, whereas cation geotemperatures partly preserve higher temperatures from the deeper, flanking basins. This study demonstrates how the thermal regime and hydrodynamics of an area can be characterised using a sparse dataset, thus representing a novel and effective methodology for regions anomalous to this central Australian example.     

Geochemistry of thermal waters on the island of Ischia (Campania, Italy)

The stratigraphic and structural situation on the island of Ischia (southern Italy), the recent volcanic activity and the presence of hot springs and fumaroles, suggest the existence of a geothermal field. The chemical and isotopic compositions of the waters from several springs and wells were examined to obtain information on deep temperatures and to formulate a geothermal model of the island. δD values range from −33.60 to −12.50‰ and δ¹⁸O from −7.10 to −1.71‰, relative to SMOW. These variations have mainly been attributed to the presence of seawater, as confirmed by the general shift to more positive values with the increase of Cl content. Water-rock reactions, evaporation and subsurface boiling also contribute to the δ¹⁸O−δD trend. The chemical analyses reveal the presence of alkaline sulphate chloride water (seawater), bicarbonate waters and waters interpreted as the result of mixing. The chemical and isotopic composition of the latter are dependent on water-rock interactions, water circulation rates and eventual evaporation and condensation phenomena. The silica geothermometer, which seems to be the most suitable for determining the deep temperatures of these waters, gave values of about 200°C, even for mixing models. Our data suggest the following geothermal model: the heat flow heats up a deep reservoir, causing steam to rise through faults and fractures and transfer heat to a shallower aquifer. The temperatures of 200°C obtained by the geothermometers are not the maximum reservoir temperatures, but are probably water-rock equilibrium temperatures for the shallower aquifers. The high boron contents and the isotopic data confirm the presence of steam in the system.     

Hydrothermal alteration in the Aluto-Langano geothermal field, Ethiopia

The hydrothermal mineral assemblages found in eight wells (with a depth range of 1320–2500 m) of the active geothermal field of Aluto-Langano (Ethiopia) indicate a complex evolution of water-rock interaction processes. The zone of upflow is characterized by high temperatures (up to 335°C) and the presence of a propylitic alteration (epidote, calcite, quartz and chlorite, as major phases) coexisting with calcite and clay minerals. The zone of lateral outflow is characterized by mixing of deep and shallow waters and the occurrence of a calcite-clay alteration that overprints a previous propylitic assemblage. Clay minerals have a mushroom-shaped zonal distribution consistent with the present thermal structure of the field. Microprobe analyses have been carried out on chlorite and illite in order to apply several geothermometers. Most of the chlorite is iron-rich chlorite. It is found that the temperatures calculated from the chlorite geothermometer (159–292°C) after Cathelineau and Nieva [Contrib. Mineral. Petrol. 91, 235–244 (1985)] are in good agreement with in-hole measured temperatures (155–300°C). In the upflow zone, temperatures calculated from this geothermometer (217–292°C), together with fluid inclusion data of Valori et al. [Eur. J. Mineral. 4, 907–919 (1992)], and computed saturation indices of alteration minerals, indicate thermal stability or slight heating. On the other hand, evidence of a significant cooling process (up to 171°C) in the outflow zone is provided by the comparison between fluid inclusion homogenization temperature (240–326°C) and in-hole temperature (155–250°C). The apparent salinities (0.8–2.3 wt% NaCl eq.) of the fluid inclusions are generally higher than the salinity of the present reservoir fluid (0.29–0.36 wt% NaCl eq.). Clay minerals (illite, smectite, Ill/S mixed layers, vermiculite and chloritic intergrades) generally occur at temperatures consistent with their stability fields.     

Sodium/lithium ratio in water applied to geothermometry of geothermal reservoirs

We propose here a new geothermometer for natural waters. Analyses from many explored geothermal fields allow us to define two empirical thermometric relationships.One is for waters of low to moderate salinity (Cl⁻< 0·3 M) log Na/Li = 1000/T −0·38 and one for marine waters and brines (Cl⁻ > 0·3 M) log Na/Li = 1195/T + 0·38 These relationships, which at present are not well understood, result mainly from the increase of Li concentrations in waters with temperature.Equation (a) proved to be adequate for spring waters from mostly known geologic origin; this is an important feature in geochemical surveys for geothermal prospecting.Furthermore, when comparison between springs and drillhole chemistry of a given geothermal field is possible, the Na/Li geothermometer gives more reliable temperature estimates from the spring compositions than do classical geothermometers.     

Isotopic and chemical composition of parbati valley geothermal discharges, North-West Himalaya, India

The isotopic compositions of the waters discharged from Parbati Valley geothermal areas indicate a higher altitude meteoric origin, with discharge temperatures reflecting variations in the depth of penetration of the waters to levels heated by the existence of a ‘normal’ geothermal gradient. On the basis of mixing models involving silica, tritium, discharge temperatures and chloride contents, deep equilibration temperatures of 120–140°C were obtained for Manikaran, possibly reaching 160°C at even greater depth. Geothermometers based on sulfate-water ¹⁸O exchange and gas reactions point to similar temperatures. Exceptionally high helium contents of the discharges correspond to apparent crustal residence times of the waters in the order of 10–100 Ma; relative nitrogen-argon contents support a largely meteoric origin of the waters with a possible fossil brine, but no detectable magmatic component.     

Geochemistry of the thermal waters of Salbardi and Tatapani, India

Geochemical studies have been carried out on water samples collected from Tatapani and Salbardi hot springs. The waters of these hot springs are classified as NaHCO₃ type. Waters in deep aquifers are associated with quartz, shale and clay terrains. Activity studies of the minerals and the waters present in the aquifers suggest that the thermal waters are within equilibrium with montmorillonite, kaolinite and quartz at about 150°C. The geochemical thermometers also estimate 150 ± 10°C as aquifer temperatures for Tatapani and Salbardi.     

Geochemical study of fluids on Lesbos island, Greece

Sixty-five water samples and seven associated gas samples have been collected on Lesbos island. The lithology and structural setting have resulted in two main types of hydrological circulation: a shallow circulation hosting low-salinity cold waters and a deeper one, hosting high-salinity hot waters that often emerge in thermal springs near the coast. The cold waters are characterized by Ca(Mg)-HCO₃(SO₄) composition, while the thermal waters generally have an Na-Cl composition. The chemical features of the former can be explained by their circulation in the ophiolite-bearing phyllitic basement and volcanic rocks. Waters circulating in the ultramafic layers of the basement are richer in Mg than the waters whose circulation is mainly within marble levels or volcanic rocks. The Na-Cl thermal waters are characterized by salinities ranging from 1910 to 35,700 mg/kg. As indicated by previous hydrogeochemical and isotopic studies, the Na-Cl composition of the thermal waters on Lesbos is the result of mixing between shallow meteoric waters and marine waters. While interacting with the minerals of the geothermal reservoir, the saline waters retain the Na/Cl sea water ratio but become enriched in Ca²⁺ and depleted in Mg²⁺ with respect to sea water.Processes of hydrothermal alteration at depth are activated by a gas phase enriched in CO₂, which reaches the geothermal reservoir by rising along the deep fractures of the basement. Thermodynamic calculations based on hydrothermal alteration processes occurring at the estimated temperatures of the geothermal reservoir (about 120 °C) indicate that the thermal waters of Lesbos are in equilibrium with talc and dolomite.     

Occurrence and significance of anomalous chloride waters at the Orakei Korako geothermal field, Taupo Volcanic Zone, New Zealand

Water with Cl concentrations from 15 to almost 10,000 mg/kg, and molecular SO₄/Cl ratios ranging from 0.003 to 1.87, drips periodically from the roof of Ruatapu cave and a side chamber, Rahu Rahu, located in the Orakei Korako geothermal field, Taupo Volcanic Zone, New Zealand. Pools in the bottom of both Ruatapu and Rahu Rahu contain sulfate–chloride waters with pH values ranging from 2.5 to 3.0; their Cl contents have varied temporally from 120 to 240 mg/kg and their molecular SO₄/Cl ratios from 0.86 to 1.30. The Cl in the water dripping from the cave roof cannot come directly from the alkali chloride–bicarbonate water that circulates in the reservoir at Orakei Korako since the modern and historic piezometric surfaces are several meters below the cave roof. Nor does all the Cl in the cave pool waters derive from the reservoir fluid as the volume input required is incompatible with their Na and K contents. A more likely source for the Cl is one whereby rain water, percolating through the fractured rhyolitic country rock, dissolves Cl present either in glass shards or halite deposited in prehistoric times when trapped alkali chloride water boiled to dryness. Given that Cl in the cave pool waters is therefore supplied from a source above rather than, as previously assumed, below, the axiom that Cl present in acid sulfate–chloride ± bicarbonate waters is necessarily a signature of a deep water or magmatic input needs qualification.     

A reconnaissance geochemical study of thermal waters of south and central Vietnam

Chemical and isotopic data of thermal springs and wells indicate that some thermal water circuits in central and south Vietnam can reach temperatures of geothermal interest (150–200°C) in zones of normal-to-slightly anomalous thermal gradients. The low gas content and the low CO₂ and H₂S concentrations suggest that there is no contribution from a magmatic source. The geothermometry results indicate that the geothermal resources in south and central Vietnam are of medium enthalpy. These results confirm those of previous geochemical surveys and indicate that the most promising geothermal sites in Vietnam are Le Thuy, south of Dong Hoi and Mo Duc near Quang Nghai.     

Chemical and isotopic composition of geothermal discharges from the Puyehue-Cordón Caulle area (40.5°S), Southern Chile

The Puyehue-Cordón Caulle area (40.5°S) hosts one of the largest active geothermal systems of Southern Chile, comprising two main thermal foci, Cordón Caulle and Puyehue. Cordón Caulle is a NW-trending volcanic depression dominated by fumaroles at the top (1500 m) and boiling springs at the northwest end (1000 m). In the latter, the alkaline-bicarbonate composition of the springs with low Mg (<0.06 mg/l) relative to the local meteoric waters (5 mg/l), low chloride (<60 mg/l), high silica (up to 400 mg/l) and δ¹⁸O–δD values close to the Global Meteoric Water Line (GMWL), in combination with the large outflow (100 l/s), suggest the existence of a secondary steam-heated aquifer overlying a main vapor-dominated system at Cordón Caulle. Subsurface temperatures of the secondary aquifer are estimated to be about 170–180 °C (corrected silica geothermometers). The Puyehue thermal area, on the other hand, includes Mg-rich hot springs discharging along stream valleys, with maximum temperatures of 65 °C and a δ¹⁸O–δD signature resembling the local meteoric composition, which suggests that the surface manifestations contain a reservoir component that is strongly diluted by meteoric waters. Topographic/hydrologic and chemical characteristics suggest that Cordón Caulle and Puyehue represent two separate upflows.