Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

Hydrogeochemical outline of thermal waters and geothermometry applications in Anatolia (Turkey)

The chemical compositions of a total of 120 thermal water samples from four different tectonically distinct regions (Central, North, East and West Anatolia) of Turkey are presented and assessed in terms of geothermal energy potential of each region through the use of chemical geothermometers. Na–Ca–HCO₃ type waters are the dominant water types in all the regions except that Na–Cl type waters are typical for the coastal areas of West Anatolia and for a few inland areas of West and Central Anatolia where deep water circulation exists. The discharge temperature of the springs ranges up to 100°C, and the bottom-hole temperatures in drilled wells up to 232°C. Geothermometry applications yield reservoir temperatures of about 125°C for Central Anatolia, 110°C for North Anatolia, 136°C for East Anatolia and 251°C for West Anatolia, the latter agreeing with some of the bottom hole temperatures measured in drilled wells. The results reveal that the highest geothermal energy potential in Turkey is associated with the West Anatolian extensional tectonics which provides a regional, deep-seated heat source and a widespread graben system allowing deep circulation of waters. The North Anatolian region, bounded to the south by the dextral North Anatolian Fault along which most of the geothermal sites are located, has the lowest energy potential, probably due to the restriction of the heat source to local magmatic activities confined to pull-apart basins. The East Anatolian region (undergoing contemporary compression) and the Central Anatolian region (where the compressional regime in the east is converted to the extensional regime in the west) have moderate energy potential. Although the recently active volcanoes suggest the presence, at depth, of still cooling magma chambers that are potential heat sources, the lack of well-developed fault systems is probably responsible for the comparatively low energy potential of these regions. Almost all the thermal waters of Turkey are saturated with respect to calcite and, hence, have a significant calcite scaling potential which is particularly high for West Anatolian waters.     

Geochemistry of the thermal springs and fumaroles of Basse-Terre Island,Guadeloupe, Lesser Antilles

 The purpose of this work was to study jointly the volcanic-hydrothermal system of the high-risk volcano La Soufrière, in the southern part of Basse-Terre, and the geothermal area of Bouillante, on its western coast, to derive an all-embracing and coherent conceptual geochemical model that provides the necessary basis for adequate volcanic surveillance and further geothermal exploration. The active andesitic dome of La Soufrière has erupted eight times since 1660, most recently in 1976–1977. All these historic eruptions have been phreatic. High-salinity, Na–Cl geothermal liquids circulate in the Bouillante geothermal reservoir, at temperatures close to 250  °C. These Na–Cl solutions rise toward the surface, undergo boiling and mixing with groundwater and/or seawater, and feed most Na–Cl thermal springs in the central Bouillante area. The Na–Cl thermal springs are surrounded by Na–HCO₃ thermal springs and by the Na–Cl thermal spring of Anse à la Barque (a groundwater slightly mixed with seawater), which are all heated through conductive transfer. The two main fumarolic fields of La Soufrière area discharge vapors formed through boiling of hydrothermal aqueous solutions at temperatures of 190–215  °C below the "Ty" fault area and close to 260  °C below the dome summit. The boiling liquid producing the vapors of the Ty fault area has δD and δ¹⁸O values relatively similar to those of the Na–Cl liquids of the Bouillante geothermal reservoir, whereas the liquid originating the vapors of the summit fumaroles is strongly enriched in ¹⁸O, due to input of magmatic fluids from below. This process is also responsible for the paucity of CH₄ in the fumaroles. The thermal features around La Soufrière dome include: (a) Ca–SO₄ springs, produced through absorption of hydrothermal vapors in shallow groundwaters; (b) conductively heated, Ca–Na–HCO₃ springs; and (c) two Ca–Na–Cl springs produced through mixing of shallow Ca–SO₄ waters and deep Na–Cl hydrothermal liquids. The geographical distribution of the different thermal features of La Soufrière area indicates the presence of: (a) a central zone dominated by the ascent of steam, which either discharges at the surface in the fumarolic fields or is absorbed in shallow groundwaters; and (b) an outer zone, where the shallow groundwaters are heated through conduction or addition of Na–Cl liquids coming from hydrothermal aquifer(s). Received: 9 November 1998 / Accepted: 15 July 1999     

Evaluation of reservoir temperatures and local utilization of geothermal waters of the Konkan Coast, India

Geochemical studies on fifteen geothermal manifestations (38–70°C) from the Konkan coast geothermal province of India have been used to evaluate the reservoir temperatures. Activity studies of the minerals and the waters present in the reservoirs suggest that the thermal waters are in equilibrium with montmorillonite, kaolinite and quartz at about 100°C. Reservoir temperatures of these geothermal systems as estimated by geochemical thermometers, are 88 to 128°C, and thus too low for economic electricity production.     

Geochemistry, geothermics and relationship to active tectonics of Gujarat and Rajasthan thermal discharges, India

Most thermal spring discharges of Rajasthan and Gujarat in northwestern India have been sampled and analysed for major and trace elements in both the liquid and associated gas phase, and for ¹⁸O/¹⁶O, D/H (in water), ³He/⁴He and ¹³C/¹²C in CO₂ (in gas) isotopic ratios. Most thermal springs in Rajasthan are tightly associated to the several regional NE–SW strike-slip faults bordering NE–SW ridges formed by Archaean rocks at the contact with Quaternary alluvial and aeolian sedimentary deposits of the Rajasthan desert. Their Ca–HCO₃ immature character and isotopic composition reveals: (1) meteoric origin, (2) relatively shallow circulation inside the crystalline Archaean formations, (3) very fast rise along faults, and (4) deep storage temperatures of the same order of magnitude as discharging temperatures (50–90°C). Thermal spring discharges in Gujarat are spread over a larger area than in Rajasthan and are associated both with the NNW–SSE fault systems bordering the Cambay basin and the ENE–WSW strike-slip fault systems in the Saurashtra province, west of the Cambay basin. Chemical and isotopic compositions of springs in both areas suggest a meteoric origin of deep thermal waters. They mix with fresh or fossil seawater entering the thermal paths of the spring systems through both the fault systems bordering the Cambay basin, as well as faults and fractures occurring inside the permeable Deccan Basalt Trap in the Saurashtra province. The associated gas phase, at all sampled sites, shows similar features: (1) it is dominated by the presence of atmospheric components (N₂ and Ar), (2) it has high crustal ⁴He enrichment, (3) it shows crustal ³He/⁴He signature, (4) it has low CO₂ concentration, and (5) the only analysed sample for ¹³C/¹²C isotopic ratio in CO₂ suggests that CO₂ has a strong, isotopically light organic imprint. All these features and chemical geothermometer estimates of spring waters suggest that any active deep hydrothermal system at the base of the Cambay basin (about 2000–3000 m) has low-to-medium enthalpy characteristics, with maximum deep temperature in the storage zone of about 150°C. In a regional overview, both thermal emergences of Rajasthan and Gujarat could be controlled by the counter-clockwise rotation of India.     

Chemical equilibria of thermal waters for the application of geothermometers from the Guanzhong basin, China

In this study, representative samples from thermal wells and springs were chemically analyzed and geothermometers were used to calculate the deep temperatures of geothermal reservoirs on the basis of water–mineral equilibrium. In some cases, however, the chemical components are not in equilibrium with the minerals in the reservoir. Therefore, log(Q/K) diagrams are used to study the chemical equilibrium for the minerals that are likely to participate. The Na–K–Mg triangular diagram is also applied to evaluate the equilibrium of water with reservoir rocks. Standard curves at the reference temperatures are prepared to reveal which type of silica geothermometer is appropriate for the specified condition. This study shows that water samples from geothermal wells W9 and W12 are in equilibrium with the selective minerals, and chalcedony may control the fluid–silica equilibrium. It is estimated that there is an exploitable low-temperature reservoir with possible temperatures of 80–90°C in the Guanzhong basin.     

Vent fluid chemistry in Bahía Concepción coastal submarine hydrothermal system, Baja California Sur, Mexico

Shallow submarine hydrothermal activity has been observed in the Bahía Concepción bay, located at the Gulf coast of the Baja California Peninsula, along faults probably related to the extensional tectonics of the Gulf of California region. Diffuse and focused venting of hydrothermal water and gas occurs in the intertidal and shallow subtidal areas down to 15 m along a NW–SE-trending onshore–offshore fault. Temperatures in the fluid discharge area vary from 50 °C at the sea bottom up to 87 °C at a depth of 10 cm in the sediments.Chemical analyses revealed that thermal water is enriched in Ca, As, Hg, Mn, Ba, HCO₃, Li, Sr, B, I, Cs, Fe and Si, and it has lower concentrations of Cl, Na, SO₄ and Br than seawater. The chemical characteristics of the water samples indicate the occurrence of mixing between seawater and a thermal end-member. Stable isotopic oxygen and hydrogen composition of thermal samples plot close to the Local Meteoric Water Line on a mixing trend between a thermal end-member and seawater. The composition of the thermal end-member was calculated from the chemistry of the submarine samples data by assuming a negligible amount of Mg for the thermal end-member. The results of the mixing model based on the chemical and isotopic composition indicate a maximum of 40% of the thermal end-member in the submarine vent fluid.Chemical geothermometers (Na/Li, Na–K–Ca and Si) were applied to the thermal end-member concentration and indicate a reservoir temperature of approximately 200 °C. The application of K–Mg and Na/Li geothermometers for vent fluids points to a shallow equilibrium temperature of about 120 °C.Results were integrated in a hydrogeological conceptual model that describes formation of thermal fluids by infiltration and subsequent heating of meteoric water. Vent fluid is generated by further mixing with seawater.     

Aquifer chemistry of the Puga and Chumatang high temperature geothermal systems in India

Results of a chemical study of the fluids from drill holes and hot springs of Puga and Chumatang areas in the northwestern part of the Himalaya are presented and discussed in this paper. The thermal waters of Puga and Chumatang are of Na-HCO₃-Cl and Na-HCO₃ types, respectively. A comparison between these waters, their chemical classification and activity studies suggest a flow path within a quartzitic-schistose basement, containing quartz, K-feldspar and illite, and in clayey terrains containing montmorillonite and illite.The chemistry of thermal waters also indicate their association with magmatic activity. The chemical geothermometers indicate the possible existence of a geothermal reservoir at Puga with temperature ≈250°C. The Chumatang area has a comparatively cooler reservoir with a temperature of 150–180°C.     

Chemical and isotopic investigation of warm springs associated with normal faults in Utah

Thermal springs associated with normal faults in Utah have been analyzed for major cations and anions, and oxygen and hydrogen isotopes. Springs with measured temperatures averaging greater than 40°C are characterized by Na + K- and SO₄ + Cl-rich waters containing 10³ to 10⁴ mg/l of dissolved solids. Lower temperature springs, averaging less than 40°C, are more enriched in Ca + Mg relative to Na + K. Chemical variations monitored through time in selected thermal springs are probably produced by mixing with non-thermal waters. During the summer months at times of maximum flow, selected hot springs exhibit their highest temperatures and maximum enrichments in most chemical constituents.Cation ratios and silica concentrations remain relatively constant through time for selected Utah thermal springs assuring the applicability of the geothermometer calculations regardless of the time of year. Geothermometer calculations utilizing either the quartz (no steam loss), chalcedony or Mg-corrected Na/K/Ca methods indicate that most thermal springs in Utah associated with normal faults have subsurface temperatures in the range of 25 to less than 120°C. This temperature range suggests fluid circulation is restricted to depths less than about three kilometers assuming an average thermal gradient of about 40°C/km.Thermodynamic calculations suggest that most thermal springs are oversaturated with respect to calcite, quartz, pyrophyllite, (Fe, Mg)-montmorillonite, microcline and hematite, and undersaturated with respect to anhydrite, gypsum, fluorite and anorthite. Chalcedony and cristobalite appear to be the only phases consistently at or near saturation in most waters. Theoretical evaluation of mixing on mineral saturation trends indicates that anhydrite and calcite become increasingly more undersaturated as cold, dilute groundwater mixes with a hot (150°C), NaCl-rich fluid. The evolution of these thermal waters issuing from faults appears to be one involving the dissolution of silicates such as feldspars and micas by CO₂-enriched groundwaters that become more reactive with increasing temperature and/or time. Solution compositions plotted on mineral equilibrium diagrams trend from product phases such as kaolinite or montmorillonite toward reactant phases dominated by alkali feldspars.Isotopic compositions indicate that these springs are of local surface origin, either meteoric (low TDS, < 5000 mg/l) or connate ground water (high TDS, > 5000 mg/l). Deviations from the meteoric water line are the result of rock-water isotopic exchange, mixing or evaporation. Fluid source regions and residence times of selected thermal spring systems (Red Hill, Thermo) have been evaluated through the use of a σ D-contour map of central and western Utah. Ages for waters in these areas range from about 13 years to over 500 years. These estimates are comparable to those made for low-temperature hydrothermal systems in Iceland.     

Geothermal assessment of the island of ischia (southern Italy) from isotopic and chemical composition of the delivered fluids

The Ischia geothermal system is hosted by silicic rocks of the Quaternary Potassic Roman Province, in southern Italy. Exploration drilling down to 1156 m depth in the mid-1950s provided information on boiling profiles (up to 250°C) and on the depth and permeability of the potential reservoirs. Discharge fluid samples were collected and analyzed to define the inflow of surrounding seawater (C1 ranges from 2.5 to 20 g/kg) into the system.Analyses of samples from surface manifestations and shallow wells collected during 1983 and 1988 point to the existence of three distinct mixing regimes, involving three water components. A dishomogeneous body of diluted water (Cl less than 2.5 g/kg), that occurs at depths > 700 m and reequilibrates at 240°C at least, is overlain by an aquifer of groundwater variably mixed with variably seawater (Cl from 4 to 10 g/kg), which tends to reequilibrate at 160°C. Steam-heated waters locally develop and act as dilutants of the rising geothermal fluids.Dilution, mixing, and evaporation of the ascending chloride fluids are supported by oxygen and hydrogen isotopic data the thermal waters being enriched in ¹⁸O and D with respect to local meteoric water by up to 7 and 30‰, respectively. The relative composition of the major cations in thermal solutions was used to discriminate the two main groups of thermal waters, the reservoir temperatures of which are estimated from the Na/K-gethermometer. K-Mg geothermometer indicates reequilibration in near-surface conditions.The isotopic composition of the fumarolic steam varies from −7 to −12‰ in ∂⁸O and from − 35 to − 70‰ in ∂D, in agreement with a deep mixed fluid that boils adiabatically from 240 to 80°C. The deuterium content of the H₂O-H₂ pair gives enrichment factor of about 830‰, corresponding to equilibrium temperature conditions slightly higher than the surface boiling temperatures. The ∂¹³C of CO₂is almost constant at −4.5‰ (1δ=0.4), suggesting an important magmatic contribution, and the ∂¹⁸O values of CO₂appears to in equilibrium with accompanying steam at the measured temperatures.The CO₂/Ar and H₂/Ar chemical ratios have been used to derive aquifer temperatures, the values obtained being consistent with those of solute geothermometers.     

Evaluation of groundwater hydrochemical characteristics and mixing behavior in the Daying and Qicun geothermal systems,Xinzhou Basin

This paper examines groundwater hydrochemical characteristics during mixing between thermal and non-thermal groundwater in low-to-medium temperature geothermal fields. A case study is made of Daying and Qicun geothermal fields in the Xinzhou basin of Shanxi province, China. The two geothermal fields have similar flow patterns, with recharge sourced from precipitation in mountain areas heated through a deep cycle, before flowing into overlying Quaternary porous aquifers via fractures. Hydrochemical features of 60 ground- and surface water samples were examined in the context of hydrogeologic information. The average temperatures of the deep geothermal reservoirs are estimated to be 125 °C in Daying field, and 159 °C in Qicun field, based on Na–K–Mg geothermometry, while slightly lower estimates are obtained using silica geothermometers. Hydrochemical features of thermal water are distinct from cold water. Thermal groundwater is mainly Cl·SO₄–Na type, with high TDS, while non-thermal groundwater is mostly HCO₃–Ca·Mg and HCO₃–Ca type in the Daying and Qicun regions, respectively. Hydrogeochemical processes are characterized by analyzing ion ratios in various waters. Higher contents of some minor elements in thermal waters, such as F, Si, B and Sr, are probably derived from extended water–rock interaction, and these elements can be regarded as indicators of flow paths and residence times. Mixing ratios between cold and thermal waters were estimated with Cl, Na, and B concentrations, using a mass balance approach. Mixing between ascending thermal waters and overlying cold waters is extensive. The proportion of water in the Quaternary aquifer derived from a deep thermal source is lower in Daying geothermal field than in Qicun field (5.3–7.3% vs. 6.3–49.3%). Mixing between thermal and non-thermal groundwater has been accelerated by groundwater exploitation practices and is enhanced near faults. Shallow groundwater composition has also been affected by irrigation with low-temperature thermal water.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

The use of mixing models and chemical geothermometers for estimating underground temperatures in geothermal systems

Application of various chemical geothermometers and mixing models indicate underground temperatures of 260°C, 280°C and 265°C in the Geysir, Hveravellir and Landmannalaugar geothermal fields in Iceland, respectively. Mixing of the hot water with cold water occurs in the upflow zones of all these geothermal systems. Linear relations between chloride, boron and δ¹⁸O constitute the main evidence for mixing, which is further substantiated by chloride, silica and sulphate relations in the Geysir and Hveravellir fields.A new carbonate-silica mixing model is proposed which is useful in distinguishing boiled and non-boiled geothermal waters. This model can also be used to estimate underground temperatures using data from warm springs. This model, as well as the chloride-enthalpy model and the Na-Li, and CO₂-gas geothermometers, invariably yield similar results as the quartz geothermometer sometimes also does. By contrast, the Na-K and the Na-K-Ca geothermometers yield low values in the case of boiling hot springs, largely due to loss of potassium from solution in the upflow. The results of these geothermometers are unreliable for mixed waters due to leaching subsequent to mixing.     

Evaluation of volcanic gas analysis from surtsey volcano, iceland 1964–1967

Methods used previously to remove compositional modifications from volcanic gas analyses for Mount Etna and Erta'Ale lava lake have bean employed to estimate the gas phase composition at Nyiragongo lava lake, based on samples obtained in 1959. H₂O data were not reported in 11 of the 13 original analyses. The restoration methods have been used to estimate the H₂O contents of the samples and to correct the analyses for atmospheric contamination, loss of sulfur and for pre- and pest-collection oxidation of H₂S, S₂, and H₂. The estimated gas compositions are relatively CO₂-rich, low in total sulfur and reduced. They contain approximately 35–50% CO₂ 45–55% H₂O, 1–2% SO₂, 1–2% H₂., 2–3% CO, 1.5–2.5% H₂S, 0.5% S₂ and 0.1% COS over,he collection temperature range 102° to 960° C. The oxygen fugacities of the gases are consistently about half an order of magnitude below quartz-magnetite-fayalite. The low total sulfur content and resulting low atomic S/C of the Nyiragongo gases appear to be related to the relatively low f_O2 of the crystallizing lava. At temperatures above 800°C and pressures of 1–1.5 k bar, the Nyiragongo gas compositions resemble those observed in primary fluid inclusions believed to have formed at similar temperatures and pressures in nephelines of intrusive alkaline rocks. Cooling to 300°C, with f_O2 buffered by the rock, results in gas compositions very rich in CH₄ (50–70%) and resembling secondary fluid inclusions formed at 200–500°C in alkaline rocks. Below 600°C the gases become supersaturated in carbon as graphite. These inferences are corroborated by several reports of hydrocarbons in plutonic alkaline rocks, and by the presence of CH₄-rich waters in Lake Kivu — a lake on the flanks of Nyiragongo volcano.     

Geochemical and hydrogeological characterization of thermal springs in Western Sicily, Italy

Thermal and cold waters from Castellammare–Alcamo (Western Sicily-Italy) were collected between May 1994 and May 1995 and studied for their chemical and isotopic composition. During the same period, mean monthly samples of meteoric water were also collected and measured for their isotopic composition. The main purpose of this study was the characterization of the acquifers and, if possible, of their recharge areas. According to the results obtained, the acquifers were divided into three main groups: (a) selenitic waters, (b) cold carbonatic waters, and (c) deep thermal waters resulting from the mixing of the other two types. Besides a mixing process between carbonatic and selenitic waters, contamination processes of thermal waters by seawater take place during their ascent. The water temperature of the acquifer feeding the thermal springs was estimated by means of various geothermometers to range between 60°C and 97°C. Isotope data on rainwater samples show a wide seasonal variation of both δ and δD values. The fairly constant values of thermal waters through time and the lack of an apparent correlation with the isotopic values of rainwater suggest the existence of a deep circuit determining an almost complete homogenisation of the seasonal variations of the isotopic values.     

Origin and evolution of two contrasting thermal groundwaters (CO2-rich and alkaline) in the Jungwon area,South Korea: Hydrochemical and isotopic evidence

In the Jungwon area, South Korea, two contrasting types of deep thermal groundwater (around 20–33 °C) occur together in granite. Compared to shallow groundwater and surface water, thermal groundwaters have significantly lower δ¹⁸O and δD values (> 1‰ lower in δ¹⁸O) and negligible tritium content (mostly < 2 TU), suggesting a relatively high age of these waters (at least pre-thermonuclear period) and relatively long subsurface circulation. However, the hydrochemical evolution yielded two distinct water types. CO₂-rich water (P_CO2 = 0.1 to 2 atm) is characterized by lower pH (5.7–6.4) and higher TDS content (up to 3300 mg/L), whereas alkaline water (P_CO2 = 10^− 4.1–10^− 4.6 atm) has higher pH (9.1–9.5) and lower TDS (< 254 mg/L). Carbon isotope data indicate that the CO₂-rich water is influenced by a local supply of deep CO₂ (potentially, magmatic), which enhanced dissolution of silicate minerals in surrounding rocks and resulted in elevated concentrations of Ca²⁺, Na⁺, Mg²⁺, K⁺, HCO₃⁻ and silica under lower pH conditions. In contrast, the evolution of the alkaline water was characterized by a lesser degree of water–rock (granite) interaction under the negligible inflow of CO₂. The application of chemical thermometers indicates that the alkaline water represents partially equilibrated waters coming from a geothermal reservoir with a temperature of about 40 °C, while the immature characteristics of the CO₂-rich water resulted from the input of CO₂ in Na–HCO₃ waters and subsequent rock leaching.     

Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

δ⁸⁷Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO₃-type groundwater prevails. δ⁸⁷Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ⁸⁷Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ⁸⁷Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ⁸⁷Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr²⁺. In contrast, more than 95% of Sr²⁺ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO₃-type groundwater. The surprisingly high content of carbonate-derived Sr²⁺ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.     

Hydrogeochemistry and environmental impact of geothermal waters from Yangyi of Tibet,China

The Yangyi geothermal field, located 72 km northwest to Lhasa City, capital of Tibet, has a high reservoir temperature up to at least 207.2 °C. The geothermal waters from both geothermal wells and hot springs belong to the HCO₃ (+CO₃)–Na type. Factor analysis of all the chemical constituents shows that they can be divided into two factors: F₁ factor receives the contributions of SO₄²⁻, Cl⁻, SiO₂, As, B, Na⁺, K⁺, and Li⁺; whereas F₂ factor is explained by HCO₃⁻, F⁻, CO₃²⁻, Ca²⁺, and Sr²⁺. The F₁ factor can be regarded as an indicator of the reservoir temperature distribution at Yangyi, but its variable correlation with the results of different geothermometers (Na–K, quartz and K–Mg) does not allow one to draw further inferences. Different from F₁, the F₂ factor is an indicator of a group of hydrogeochemical processes resulting from the CO₂ pressure decrease in geothermal water during its ascent from the deep underground, including transformation of HCO₃⁻ to CO₃²⁻, precipitation of Ca²⁺ and Sr²⁺, and release of F⁻ from some fluoride-bearing minerals of reservoir rocks. The plot of enthalpy vs. chloride, prepared on the basis of Na–K equilibrium temperatures, suggests that a parent geothermal liquid (PGL) with Cl⁻ concentration of 185 mg/L (that of sample YYT-8) and enthalpy of 1020 J/g (corresponding to a temperature of 236–237 °C, i.e., somewhat higher than that of sample YYT-6) is present in the geothermal reservoir of the Yangyi area, below both the Qialagai valley and the Bujiemu valley, although the samples less affected by mixing and cooling (YYT-6 and YYT-7) come from the second site. The discharge of geothermal waters with high contents of toxic elements such as B, As and F into the Luolang River, the only drinking water source for local residents, has caused slight pollution of the river water. Great care should therefore be taken in the geothermal water resource management at Yangyi.     

Evidence from fluid inclusions for a paleogeothermal gradient at the geothermal test well sites, Los Alamos, New Mexico

Homogenization temperatures of individual fluid inclusions from the geothermal test well sites near Los Alamos, New Mexico, systematically change as a function of depth in the cores. Inclusions in samples from depths between 1.5 and 3.0 km have re-equilibrated to thermal gradients higher than the present gradient of 50–60°C/km. The loci of maximum temperatures attained has a slope of about 70°C/km; the deepest sample has cooled to 200°C from a maximum of 230°C. The wide range of salinities (0.0 wt.% equivalent NaCl to more than 25 wt.% equivalent NaCl) observed in each sample indicates a large amount of pervasive fluid circulation had not occurred at the time of re-equilibration of these inclusions. The results are relevant to calculations for the thermal history of the test site.     

Characterising the hydrothermal alteration of the Broadlands–Ohaaki geothermal system, New Zealand, using short-wave infrared spectroscopy

Hydrothermal clay minerals present in the Broadlands–Ohaaki geothermal field were characterised by field portable short-wave infrared spectroscopy. Three major alteration zones, an upper smectite, a middle illite and a lower illite–chlorite, are spectrally separable. The zoning pattern is generally consistent with the thermal structure of the geothermal field, although occasionally zone boundaries cut present-day isotherms. The data indicate that temperature is the major control on clay zoning and permeability plays a subordinate role.Both beidellite and montmorillonite are common in the upper, low-temperature smectite zone. Kaolinite, mainly of low crystallinity, marks the margin of the field where cool acidic ground waters inflow. In the middle alteration zone, illite, dominantly K-rich, shows a narrow compositional variability. Some highly permeable zones are characterised by illite with low octahedral Al contents. Ammonium-bearing illite and buddingtonite are present locally in permeable horizons within the illite zone, where temperatures are above 200°C. Chlorite is most abundant in the lower alteration zone (temperature >250°C), although it also occurs unevenly in the upper and middle alteration zones. Chlorite varies from Mg- to Fe-rich varieties (but mostly with Mg# values <0.5), but no compositional trends with respect to depth are spectrally detectable.