Hydrochemical and isotopic properties of Heybeli geothermal area (Afyon,Turkey)

The thermal waters at the Heybeli (K?z?lkirse) low-temperature geothermal field located in the Afyonkarahisar Province (western Turkey) are discharged from Paleozoic recrystallized limestone. The temperature, specific electrical conductivity, and pH values of the thermal waters are within the range of 28.9 to 54.7 °C, 587 to 3580 μS/cm, and 6.32 to 7.37, respectively. The Heybeli geothermal system is fed by meteoric waters. The waters are heated at depth by high geothermal gradient caused by the neotectonic activity in the deep and ascend to the surface through fractures and faults by convection. The thermal waters are of Na-Ca-HCO₃-SO₄ type and their chemical composition of the waters is mainly controlled by water-rock interaction and mixing processes. The δ¹⁸O, δ²H and tritium compositions show that the thermal waters are of meteoric origin and the residence time at the reservoir is longer than 50 years. Isotope data (δ³⁴S and δ¹³C) indicate recrystallized limestones as origin of CO₂ and structural substitution of sulfate into marine carbonates (CAS) as origin of sulfur. Chemical, \( {\updelta}^{18}{\mathrm{O}}_{\left({\mathrm{SO}}_4-{\mathrm{H}}_2\mathrm{O}\right)} \) isotope geothermometers and mineral equilibrium diagrams applied to thermal waters gave reservoir temperatures between 62 and 115 °C. Saturation index calculations show that the most expected minerals causing scaling at outflow conditions during the production and utilization of Heybeli geothermal waters are calcite, aragonite, dolomite, quartz, and chalcedony.     

Hydrochemical,isotopic, and reservoir characterization of the Pasinler (Erzurum) geothermal field,eastern Turkey

The reservoir temperature and conceptual model of the Pasinler geothermal area, which is one of the most important geothermal areas in Eastern Anatolia, are determined by considering its hydrogeochemical and isotope properties. The geothermal waters have a temperature of 51 °C in the geothermal wells and are of Na–Cl–HCO₃ type. The isotope contents of geothermal waters indicate that they are of meteoric origin and that they recharge on higher elevations than cold waters. The geothermal waters are of immature water class and their reservoir temperatures are calculated as 122–155 °C, and their cold water mixture rate is calculated as 32%. According to the δ¹³C_VPDB values, the carbon in the geothermal waters originated from the dissolved carbon in the groundwaters and mantle-based CO₂ gases. According to the δ³⁴S_CDT values, the sources of sulfur in the geothermal waters are volcanic sulfur, oil and coal, and limestones. The sources of the major ions (Na⁺, Ca²⁺, Mg²⁺, Cl^?, and HCO₃ ^?) in the geothermal waters are ion exchange and plagioclase and silicate weathering. It is determined that the volcanic rocks in the area have effects on the water chemistry and elements like Zn, Rb, Sr, and Ba originated from the rhyolite, rhyolitic tuff, and basalts. The rare earth element (REE) content of the geothermal waters is low, and according to the normalized REE diagrams, the light REE are getting depleted and heavy REE are getting enriched. The positive Eu and negative Ce anomalies of waters indicate oxygen-rich environments.     

Zur Barium-Strontium-Mineralisation

The baryte occurrences along N to NW striking faults in Carboniferous and Devonian strata of the Ruhr area and the Rheinisches Schiefergebirge (Western Germany) are related to still presently active chloridic, Ba-Sr bearing Na and Na-Ca solutions. These originated from deeper seated waters which have their origin in meteoric waters circulating in the fault systems, and in fossil waters from Ba-rich Ordovician strata. Experimental results of the solubility behaviour of BaSO₄ and SrSO₄ in water and in aqueous solutions can explain the Ba and Sr content of these recent and fossil brines. A theory of Ba-Sr mineralisation is presented for the Rheinisches Schiefergebirge which is believed to find general application in other regions.     

Geochemistry of the thermal waters of Sikhote Alin

This paper reports new geochemical data on the low temperature nitric thermal waters of Sikhote Alin. The studied alkaline waters belong to the HCO₃-Na type with significant trace element variations. The waters demonstrate an increase in temperature and TDS from the south northward of Sikhote Alin. The oxygen and hydrogen isotopic data suggest their infiltration origin. The chemical composition of these waters was formed by water-rock interaction.     

Hydrochemistry and gas geochemistry of the northeastern Algerian geothermal waters

This study focuses on the water and gas chemistry of the northeastern Algerian thermal waters. The helium gas was used to detect the origin of the geothermal fluid. In the Guelma Basin, the heat flow map shows an anomaly of 120 ± 20 mW/m² linked to the highly conductive Triassic extrusion. The chemical database reveals the existence of three water types, Ca-SO₄/Na-Cl, which are related to evaporites and rich in halite and gypsum minerals. The third type is Ca (Na)-HCO₃, which mostly characterizes the carbonated Tellian sector. The origin of thermal waters using a gas-mixing model indicates a meteoric origin, except for the El Biban hot spring (W10), which shows a He/Ar ratio of 0.213, thus suggesting the presence of batholith. The helium distribution map indicates a lower ³He/⁴He ratio between 0 Ra and 0.04 Ra in the W10 and W15 samples, which is compatible with the crustal ratio. Reservoir temperatures estimated by silica geothermometers give temperatures less than 133 °C. The geothermal conceptual model suggests that a geothermal system was developed by the deep penetration of infiltrated cold waters to a depth of 2.5 km and then heated by a conductive heat source (batholith for El Biban case). The thermal waters rise up to the surface through the deep-seated fractures. During their ascension, they are mixed with shallow cold groundwater, which increase the Mg content and cause the immature classification of the water samples.     

Geochemical patterns and origin of alkaline thermal waters in Central Greece (Platystomo and Smokovo areas)

This study investigates the origin and chemical composition of the thermal waters of Platystomo and Smokovo areas in Central Greece as well as any possible relationships of them to the neighboring geothermal fields located in the south-eastern part of Sperchios basin. The correlations between different dissolved salts and the temperature indicate that the chemical composition of thermal waters are controlled by, the mineral dissolution and the temperature, the reactions due to CO₂ that originates possibly by diffusion from the geothermal fields of Sperchios basin and the mixing of thermal waters with fresh groundwater from karst or shallow aquifers. Two major groups of waters are recognized on the basis of their chemistry: thermal waters of Na–HCO₃–Cl type and thermal waters mixed with fresh groundwater of Ca–Mg–Na–HCO₃ type. All thermal waters of the study area are considered as modified by water–rock interaction rainwater, heated in depth and mixed in some cases with fresh groundwater when arriving to the surface. Trace elements present low concentrations. Lithium content suggests discrimination between the above two groups of waters. Boron geochemistry confirms all the above remarks. Boron concentration ranges from 60 μg L^?1 to 10 mg L^?1, while all samples’ constant isotopic composition (δ¹¹B ≈ 10 ‰) indicates leaching from rocks. The positive correlation between the chemical elements and the temperature clearly indicates that much of the dissolved salts are derived from water–rock interactions. The application of geothermometers suggests that the reservoir temperature is around 100–110 °C. Chalcedony temperatures are similar to the emergent temperatures and this is typical of convective waters in fault systems in normal thermal gradient areas.     

Redox chemistry of uranium and iron,radium geochemistry,and uranium isotopes in the groundwaters of the Lode`ve Basin,Massif Central,France

This paper discusses the geochemistry, origin and evolution of groundwaters in the Lode`ve Basin Massif Central, France, including major and trace elements (U, Ra, Ba and Fe) and the significance of the redox potential. These groundwaters originate from thermal waters by CO₂ outgassing and mixing with meteoric waters. The measured redox potential (Eh > −50 mV) is generally controlled by the ferric oxide-Fe²⁺ equilibrium; below this potential the groundwaters are saturated with respect to FeS.Redox systems other than Fe are not necessarily at equilibrium, and this is particularly true for U. In the relatively reduced waters (Eh< 100mV), U concentrations may be controlled by coffinite or uraninite. Above 100 mV, U concentrations range from 10 to 200 ppb; they correspond either to mineral dissolution, or could be controlled by an oxidized mineral.Radium mobility is strongly dependent on SO₄ concentration, and it coprecipitates with barite. Radium probably has its origin in calcium-sodium bicarbonate type waters and is not related to U mineralization.     

Conditions of formation mineral waters in Sarissky Stiavnik and Radoma

Mineral waters in Sarissky Stiavnik and Radoma are formed on the tectonic fault zones of the Zlin formation and Makovica sandstones. Precipitation waters flow downwards thus becoming enriched in TDS content. The process is enhanced by inflow of CO₂ rich mineral waters of the Obidowa-Slopnice-Zboj unit, pushed by carbon dioxide and methane. Mineral waters in Sarissky Stiavnik and Radoma are of the Na-HCO₃ chemical type, typical for the mineral water springs of the Magura unit in this part of the flysch belt. The origin of chloride component in the TDS content can be found in the waters with thalasogenic mineralization beneath the Magura unit, where the Obidowa-Slopnice-Zboj unit is to be found. Hydrogeological structures in Sarissky Stiavnik and Radoma can be classified as combined hydrogeological structures, where the upper partial hydrogeological structure is opened (Magura unit) and the lower structure is semi-closed (unit Obidowa-Slopnice-Zboj).     

Carbonate characteristics of waters of the Arctic Ocean continental slope

Carbonate characteristics of the water mass of the deepwater part of the Arctic Ocean (AO) in the continental slope area were determined, and the range and reasons of their variability during summer-fall season were revealed. The AO water area is a meaningful sink for atmospheric carbon dioxide. The warm intermediate Atlantic waters (AW) are also undersaturated with carbon dioxide relative to its content in the atmosphere. While these waters move along AO continental slope, the value pCO₂ in the AW core decreases to 8–10 μatm (mainly, due to drop in the water temperature). The potential absorption capacity of the AO deepwater basin is estimated at approximately 48 Tg of carbon (without sea ice taken into account). Joint analysis of carbonate and hydrological parameters showed that near-bottom waters formed on the shallow shelf of the Laptev Sea, which is rich in inorganic and organic carbon of terrestrial and marine genesis, take part in formation of halocline waters of the AO. They are modified due to interaction with AW penetrating to the shelf and are transferred to the deepwater AO segment, where they occur in the halocline according to their density. Transformed near-bottom waters of the Laptev Sea shelf, similar to waters of the halocline of Pacific origin in the eastern sector of the AO, are traced above the continental slope in Amundsen Basin on the basis of higher CO₂ concentrations.     

Diagenetic and other highly mineralized waters in the Polish Carpathians

Highly mineralized waters of different chemical types and origin occur in the flysch formations and their bedrocks in the western part of the Polish Carpathians. The marine sedimentation water of the flysch formations is not preserved, as the most mineralized and the heaviest isotopic values of flysch waters are characterized by δ¹⁸O and δ²H values in the ranges of 5–7‰ and −(20–30)‰, respectively. Their origin is related to the dehydration of clay minerals during burial diagenesis, with molecules of marine water completely removed by molecules of released bound water. They are relatively enriched in Na⁺ in respect to the marine water, supposedly due to the release of Na⁺ during the illitization of smectites and preferable incorporation of other cations from the primary brine into newly formed minerals. In some parts of younger formations, i.e. in the Badenian sediments, brines occur with isotopic composition close to SMOW and Cl⁻ contents greatly exceeding the typical marine value of about 19.6 g/L, supposedly due to ultrafiltration. Most probably, the marine water of the flysch formations was similarly enriched chemically in its initial burial stages. Final Cl⁻ contents in diagenetic waters depend on different Cl⁻ contents in the primary brines and on relationships between diagenetic and further ultrafiltration processes. In some areas, diagenetic waters migrate to the surface along fault zones and mix with young local meteoric waters becoming diluted, with the isotope composition scattering along typical mixing lines. In areas with independent CO₂ flow from great depths, they form chloride CO₂-rich waters. Common CO₂-rich waters are formed in areas without near-surface occurrences of diagenetic waters. They change from the HCO₃–Ca type for modern waters to HCO₃–Mg–Ca, HCO₃–Na–Ca and other types with elevated TDS, Mg²⁺ and/or Na⁻ contents for old waters reaching even those of glacial age. Bedrocks of the flysch are represented by Mesozoic and Paleozoic mudstones, sandstones and carbonates, and in some areas by Badenian sediments. Brines of the Mesozoic and Paleozoic bedrocks are usually significantly enriched in Ca²⁺ and Mg²⁺ in comparison with the Badenian brines. By analogy to the deepest brines in the adjacent Upper Silesian Coal Basin, they are supposed to originate from paleometeoric waters of a hot climate.     

Tufa and travertines of southern Italy: deep‐seated,fault‐related CO2 as the key control in precipitation

Continental carbonates of Quaternary age in southern Italy commonly exhibit the facies of calcareous tufa, often reported as related to shallow aquifers fed by meteoric waters and to organic processes. A close spatial relationship exists between the mappable tufa deposits and major Quaternary extensional faults. With respect to the Ca‐Mg‐HCO₃ composition of limestone aquifers’ springs, tufa‐depositing springs exhibit higher salinity and alkalinity, are slightly warmer, have lower pH and are enriched in SO₄ and CO₂. Their δ¹³C values are systematically positive and compatible with a deep‐seated carbon source. A clear input of soil‐derived organic carbon is indicated only for small, non‐mappable tufas deposited by perched springs. The dataset indicates that the large tufa deposits owe their origin to a supplementary source of CO₂ advected by degassing through active faults, as a necessary prerequisite for inducing a rise of total dissolved salts and alkalinity. Meteoric waters that have come from a shallow aquifer are able to precipitate only limited amount of carbonates.     

Geochemical assessment,mixing behavior and environmental impact of thermal waters in the Guelma geothermal system,Algeria

A study of thirteen geothermal springs located in the geothermal field of Guelma, northeastern Algeria, was conducted. Samples were collected during the period between January 2014 and February 2016. Geochemical processes responsible for the chemical composition of thermal and mineralized water were evaluated. The hydrochemical analysis shows that the thermal waters are characterized by the presence of two different chemical facies, the first type SO₄–Ca in the east, west and south of Guelma, the second type HCO₃–Ca in the south. This analysis also attributed to sodium, chlorides, and sulfates to an evaporitic terrigenous origin by the molar ratio Sr²⁺/Ca²⁺. The thermal spring waters from Guelma geothermal system have a meteoric origin, and all samples are immature with strong mixing between hot and shallow waters with 19–38.5% rate of mixing. The silica geothermometer shows that these thermal waters have a temperature varying from 84 to 122 °C and that the water came from a depth of 2100–3000 m through a fault system that limits the pull-apart basin of Guelma. Potential environmental effluent from thermal spas could pollute in both the irrigation and drinking waters, and which imposes danger on the health of the inhabitants of the region.

     

Hydrogeochemical study of the Terme and Karakurt thermal and mineralized waters from Kirşehir Area,central Turkey

The Terme and Karakurt thermal resorts are located in the center of Kirşehir city in central Anatolia. Thermal waters with temperatures of 44–60°C are used for central heating and balneologic purposes. Paleozoic rocks of the Kirşehir Massif are the oldest units in the study area. The basement of the Massif comprises Paleozoic metamorphic schist and marbles which partly contain white quartzite layers of a few tens of cm thickness. The metamorphic schists which are cut by granites of Paleocene age are overlain by horizontally bedded conglomerate, sandstone, claystone, and limestone of upper Paleocene-Eocene age. Among the thermal and cold waters collected from the areas of Terme and Karakurt, those from thermal waters are enriched with Ca–HCO₃ and cold waters are of Ca–Mg–HCO₃ type waters. The pH values of samples are 6.31–7.04 for the thermal well waters, 6.41 for thermal spring, 7.25 and 7.29 for the cold waters, and 7.52 for the Hirla lake water. EC values are 917–2,295 μS/cm for the thermal well waters, 2,078 μS/cm for thermal spring, and 471 and 820 μS/cm for the cold springs. The lowest TDS content is from water of T10 thermal well in the Terme area (740.6 mg/l). The hot and cold waters of Terme show very similar ion contents while the Karakurt hot waters at western most parts are characterized by distinct chemical compositions. There is ion exchange in thermal waters from the T5 (5), T6 (6), T12 (7), and T1 (8) wells in the Terme area. The thermal waters show low concentrations of Fe, Mn, Ni, Al, As, Pb, Zn and Cu. Waters in the study area are of meteoric origin, and rainwater percolated downwards through faults and fractures, and are heated by the geothermal gradient, later rising to the surface along permeable zones. δ¹³C_VPDB values measured on dissolved inorganic carbon in samples range from −1.65 to +5.61‰ for thermal waters and from −11.81 to −10.15‰ for cold waters. Carbon in thermal waters is derived from marine carbonates or CO₂ of metamorphic origin while carbon in cold waters originates from freshwater carbonates.     

Origin of abnormal substances discharged from Baozhusi Dam Base, Sichuan, China

Baozhusi reservoir is a large-scale hydropower engineering project in Sichuan Province, China. After drainage wells were drilled in the dam base, white flocculent and black gel substances, accompanied by a rotten-egg odor, were found in some of the drainage water wells. On the basis of a brief introduction of the geological setting in Baozhusi Dam area, the origin of the abnormal substances were analyzed and discussed through the following procedures: (1) the abnormal substances were sampled and their chemical and mineral compositions were analyzed; (2) the origin of drainage waters were determined using the isotope method and well flux measurement results; (3) characteristics of chemical composition of drainage waters were discussed relative to other kinds of waters in the area; (4) process of formation of the abnormal substances were determined using hydrogeochemical methods; (5) laboratory immersion experiment was carried out to verify the conclusions. Results showed that the abnormal substances were formed by interactions between recharging water from the reservoir and dam base rock as well as dam building materials. Among these, the precipitation of calcite and dolomite, the dissolution of calcium hydroxide and anhydrite as well as the reduction of SO₄^–2 to H₂S by organic matter are the most important processes.     

Major and trace element compositions (including REE) of mineral,thermal, mine and surface waters in SW Germany and implications for water–rock interaction

The near-surface water cycle in a geologically complex area comprises very different sources including meteoric, metamorphic and magmatic ones. Fluids from these sources can react with sedimentary, magmatic and/or metamorphic rocks at various depths. The current study reports a large number of major, minor and trace element analyses of meteoric, mineral, thermal and mine waters from a geologically well-known and variable area of about 200 × 150 km in SW Germany. The geology of this area comprises a Variscan granitic and gneissic basement overlain in parts by Triassic and Jurassic shales, sandstones and limestones. In both the basement and the sedimentary rocks, hydrothermal mineralization occurs (including Pb, Cu, As, Zn, U, Co and many others) which were mined in former times. Mineral waters, thermal waters and meteoric waters flowing through abandoned mines (mine waters) are distributed throughout the area, although the mine waters concentrate in and around the Schwarzwald.The present analyses show, that the major element composition of a particular water is determined by the type of surrounding rock (e.g., crystalline or sedimentary rocks) and the depth from which the water originates. For waters from crystalline rocks it is the origin of the water that determines whether the sample is Na–Cl dominant (deeper origin) or Ca–HCO₃ dominant (shallow origin). In contrast, compositions of waters from sedimentary rocks are determined by the availability of easily soluble minerals like calcite (Ca–HCO₃ dominant), halite (Na–Cl dominant) or gypsum (Ca–SO₄ dominant). Major element data alone cannot, therefore, be used to trace the origin of a water. However, the combination of major element composition with trace element data can provide further information with respect to flow paths and fluid–rock interaction processes. Accordingly, trace element analyses showed, that:

• −Ce anomalies can be used as an indicator for the origin of a water. Whereas surface waters have negative or strongly negative Ce anomalies, waters originating from greater depths show no or only weak negative Ce anomalies.
• −Eu anomalies can be used to differentiate between host rocks. Waters from gneisses display positive Eu anomalies, whereas waters from granites have negative ones. Waters from sedimentary rocks do not display any Eu anomalies.
• −Rb and Cs can also be indicators for the rock with which the fluid interacted: Rb and Cs correlate positively in most waters with Rb/Cs ratios of ∼2, which suggests that these waters are in equilibrium with the clay minerals in the rocks. Rb/Cs ratios >5 indicate reaction of a water with existing clay minerals, whereas Rb/Cs ratios <2 are probably related to host rock alteration and clay mineral formation.

The chemical compositions of carbonate precipitates from thermal waters indicate that rare earth elements (REEs), Rb and Cs concentrations in the minerals are controlled by the incorporation of clay particles that adsorb these elements.     

Hydrogeochemical processes in an arid region of Europe (Almeria,SE Spain)

In the Lower Andarax river basin 3 aquifer units have been defined, namely the Carbonate Aquifer, the Deep Aquifer and the Detrital Aquifer, which between them contain a wide variety of water types. Identification of hydrogeochemical processes has been performed by studying a series of ionic ratios, comprising the principal constituents together with B and Li (Cl vs SO₄, Cl vs Mg, Cl vs Li, B vs Li). Among the processes detected, the circulation of groundwaters with high concentrations of SO₄ was found to have significant effects. Moreover, in the coastal region, naturally occurring processes related to the flushing of saline waters from sediments of marine origin occur in conjunction with others, clearly of human origin, that are related to saltwater intrusion. A further factor is the entry, from overlying deposits, of waters with a high saline content; this salinity is related to the flushing of sediments of marine origin. The use of B and Li together enables waters in which salinity is related to seawater to be distinguished from others in which salinity is related to evaporitic layers or to thermal areas. The concentration of Li is directly related to water temperature, while that of B is greater in the most saline sectors, of gypsiferous and/or seawater origin.     

Chemical and isotopic characteristics of fluids along the Cameroon Volcanic Line, Cameroon

Results of the chemical and isotopic analysis of the water and gases discharged from volcanic crater lakes and soda springs located along the Cameroon Volcanic Line were used to characterize and infer their genetic relationships. Variations in the solute compositions of the waters indicate the dominant influence of silicate hydrolysis. Na⁺ (40–95%) constitutes the major cation in the springs while Fe²⁺ + Mg²⁺ (70%) dominate in the CO₂-rich lakes. The principal anion is HCO₃ (>90%), except in the coastal springs where Cl-predominates. Lakes Nyos and Monoun have FeMgCaHCO₃⁻ type signatures; the soda springs are essentially NaHCO₃⁻ type, while all other lakes show similar ionic compositions to dilute surface waters. Dissolved gases show essentially CO₂ (>90%), with small amounts of Ar and N₂, while CH₄ constitutes the principal component in the non-gassy lakes. Active volcanic gases are generally absent, except in the Lobe spring with detectable H₂S. Stable isotope ratio evidence indicates that the bicarbonate waters are essentially of meteoric origin. CO₂ (δ¹³C = −2 to −8%₀ and He (³He/⁴He = 1 to 5.6R_a) infer a mantle contribution to the total CO₂. CH₄ has a biogenic source, while Ar and N₂ are essentially atmospheric in origin, but mixing is quite common.     

Hydrogeochemical evaluation of Umut geothermal field (SW Turkey)

Tekkehamam geothermal field is located in the South of Menderes Graben (Aegean region) and is one of the most important geothermal sites of Western Anatolia. Umut geothermal field is a part of the Tekkehamam field. This study was conducted in order to determine the origin and hydrogeochemical properties of the geothermal waters. For this purpose, sampling was done in order to check the chemistry of the water, and ¹⁸O, ²H isotope analyses done at four wells, nine natural springs and three cold water sources. According to the results of the chemical analysis, the geothermal waters were determined to be of Na + K-SO₄ type. Additionally, ¹⁴C and ³H analyses were done in selected well and spring waters for the purpose of age determination of groundwater; most of the waters were determined to be submodern. Geothermometer calculations show that the reservoir temperature for the Umut geothermal field ranges between 148 and 180 °C. Stable isotope results indicate that Umut geothermal waters are meteoric in origin. Mixing between shallow and deep waters is the dominant subsurface process that determines the physical and chemical character of the waters.     

The Pozzo del Sale Groundwaters (Irpinia, Southern Apennines, Italy): Origin and Mechanisms of Salinization

Chemical and water isotope ratios data for groundwaters from the Pozzo del Sale area in the Irpinia sector of the Southern Apennines are presented. The water chemistry of the aquifer system may initially be regarded as the result of easy and common, low temperature interaction between meteoric water and Late Messinian evaporites, which produce Ca-bicarbonate and Na-chloride passing through Ca-sulfate waters. However, a closer inspection reveals a more complicated geochemical setting consisting of: (1) two further Na-sulfate and Ca(Mg)-sulfate waters; (2) the existence of different meteoric recharge areas; (3) the mixing between the different groundwaters and allochthonous fluids from terrestrial mud volcanoes. The salinization mechanism and the local mineralogy were inferred by classical and novel ternary and binary diagrams. The presence of MgSO₄- and Na₂SO₄-bearing minerals of non-marine or mixed origin other than gypsum and halite within the local evaporites suggests a mineralogical heterogeneity within the local Messinian evaporites. The paleoenvironment of this sector of the Gessoso–Solfifera Formation might have been composed of relatively small playa-lakes fed by seawater but also large amounts of continental waters of meteoric origin.     

Origin of components in Chilean thermal waters

Thermal waters of northern (18°–27°S) and southern (37°–45°S) Chile occur in two very different climatic, geologic and hydrologic environments: arid closed basins with abundant evaporites in the north; humid climate and well drained valleys in the south. The origin and behavior of the main components of the two groups of waters are examined and compared to each other. The modeling of the alteration of volcanic rocks leads to water compositions very different from those observed both in the north and south. In addition to hydrothermal alteration and deep emanations, the Cl/Br ratio reveals a major contribution of saline waters to the two groups: infiltrating brines from salt lakes in the north; seawater in the south.In the north, concentrations of Cl, Br, Na, K, Ca, SO₄, Li, B, Si result from the mixing of alteration waters with recycled brines. Hydrothermal alteration is obscured by this massive saline input, except for Mg. δ³⁴S values are consistent with an origin of sulfate from salar brines, which are themselves derived from deep Tertiary gypsum. In the south, two processes account for the composition of thermal waters: mixing of alteration waters with seawater and deep magmatic contribution. The mixing process controls the concentration of Cl, Br, Na, Alk, Si, K, Ca, Mg. Magmatic inputs are detectable for SO₄, Li and B. δ³⁴S suggests that sulfate stems from the mixing of alteration waters with either marine SO₄ in coastal waters or with deep SO₂ in inland waters. In both the north and south, the Mg concentration is drastically lowered (<1 μmol/L) by the probable formation of a chlorite-type mineral. In the south, very small amounts of seawater (<1% in volume) are sufficient to imprint a clear signature on thermal waters. Not only coastal springs are affected by seawater mixing, but also remote inland springs, as far as 150 km from the sea. Subduction of marine sediments in the accretive margin could be the source of the marine imprint in thermal waters of southern Chile. Seawater may be expelled from the subducted lithosphere and incorporated into the mantle source.