Geochemical constraints for the origin of thermal waters from western Turkey

The combined chemical composition, B and Sr isotopes, and the basic geologic setting of geothermal systems from the Menderes Massif in western Turkey have been investigated to evaluate the origin of the dissolved constituents and mechanisms of water–rock interaction. Four types of thermal water are present: (1) a Na–Cl of marine origin; (2) a Na–HCO₃ type with high CO₂ content that is associated with metamorphic rocks of the Menderes Massif; (3) a Na–SO₄ type that is also associated with metamorphic rocks of the Menderes Massif with H₂S addition; and (4) a Ca–Mg–HCO₃–SO₄ type that results from interactions with carbonate rocks at shallow depths. The Na–Cl waters are further subdivided based on Br/Cl ratios. Water from the Cumalı Seferihisar and Bodrum Karaada systems are deep circulated seawater (Br/Cl=sea water) whereas water from Çanakkale–Tuzla (Br/Cl<sea water) are from dissolution of Messinian evaporites. Good correlations between different dissolved salts and temperature indicate that the chemical composition of the thermal waters from non-marine geothermal systems is controlled by: (1) temperature dependent water–rock interactions; (2) intensification of reactions due to high dissolved CO₂ and possibly HCl gasses; and (3) mixing with overlying cold groundwater. All of the thermal water is enriched in B. The B isotopic composition (δ¹¹B=2.3‰ to 18.7‰; n=6) can indicate either leaching of B from the rocks, or B(OH)₃ degassing flux from deep sources. The large ranges in B concentrations in different rock types as well as in thermal waters from different systems suggest the water-rock mechanism. ⁸⁷Sr/⁸⁶Sr ratios of the thermal water are used to differentiate between solutes that have interacted with metamorphic rocks (⁸⁷Sr/⁸⁶Sr ratio as high as 0.719479) and carbonate rocks (low ⁸⁷Sr/⁸⁶Sr ratio of 0.707864).     

Geochemical constraint on origin and evolution of solutes in geothermal springs in western Yunnan,China

Geothermal resources are very rich in Yunnan, China. However, source of dissolved solutes in geothermal water and chemical evolution processes remain unclear. Geochemical and isotopic studies on geothermal springs and river waters were conducted in different petrological-tectonic units of western Yunnan, China. Geothermal waters contain Ca–HCO₃, Na–HCO₃, and Na (Ca)–SO₄ type, and demonstrate strong rock-related trace elemental distributions. Enhanced water–rock interaction increases the concentration of major and trace elements of geothermal waters. The chemical compositions of geothermal waters in the Rehai geothermal field are very complicated and different because of the magma chamber developed at the shallow depth in this area. In this geothermal field, neutral-alkaline geothermal waters with high Cl, B, Li, Rb Cs, As, Sb, and Tl contents and acid–sulfate waters with high Al, Mn, Fe, and Pb contents are both controlled by magma degassing and water–rock interaction. Geothermal waters from metamorphic, granite, and sedimentary regions (except in the Rehai area) exhibit varying B contents ranging from 3.31 mg/L to 4.49 mg/L, 0.23 mg/L to 1.24 mg/L, and <0.07 mg/L, respectively, and their corresponding δ¹¹B values range from −4.95‰ to −9.45‰, −2.57‰ to −8.85‰, and −4.02‰ to +0.06‰. The B contents of these geothermal waters are mainly controlled by leaching host rocks in the reservoir, and their δ¹¹B values usually decrease and achieve further equilibrium with its surrounding rocks, which can also be proven by the positive δ¹⁸O-shift. In addition to fluid–rock reactions, the geothermal waters from Rehai hot springs exhibit higher δ¹¹B values (−3.43‰ to +1.54‰) than those yielded from other areas because mixing with the magmatic fluids from the shallow magma. The highest δ¹¹B of steam–heated waters (pH 3.25) from the Zhenzhu spring in Rehai is caused by the fractionation induced by pH and the phase separation of coexisting steam and fluids. Given the strong water–rock interaction, some geothermal springs in western Yunnan show reservoir temperatures higher than 180 °C, which demonstrate potential for electricity generation and direct-use applications. The most potential geothermal field in western Yunnan is located in the Rehai area because of the heat transfer from the shallow magma chamber.     

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

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

Boron isotope ratios of surface waters in Guadeloupe,Lesser Antilles

Large variations are reported in the B concentrations and isotopic ratios of river and thermal spring waters in Guadeloupe, Lesser Antilles. Rivers have δ¹¹B values around 40‰ and B concentrations lower than 30 μg/L, while thermal springs have δ¹¹B of 8–15‰ and B concentrations of 250–1000 μg/L. River samples strongly impacted by hydrothermal inputs have intermediate δ¹¹B and B contents. None of these surface water samples have δ¹¹B comparable to the local unweathered volcanic rocks (around 0‰), implying that a huge isotopic fractionation of 40‰ takes place during rock weathering, which could be explained by preferential incorporation of ¹⁰B during secondary mineral formation and adsorption on clays, during rock weathering or in the soils. The soil-vegetation B cycle could also be a cause for such a fractionation. Atmospheric B with δ¹¹B of 45‰ represents 25–95% of the river B content. The variety of the thermal spring chemical composition renders the understanding of B behavior in Guadeloupe hydrothermal system quite difficult. Complementary geochemical tracers would be helpful.     

B, Sr, O and H Isotopic Compositions of Formation Waters from the Bachu Bulge in the Tarim Basin

In order to elucidate the origin and migration of basinal brines in the Bachu Bulge, Tarim Basin, we have carried out analyses on chemical composition, and boron, hydrogen and oxygen isotopes of formation waters together with the XRD of clay minerals from the Paleozoic strata. The waters show Ca, B, Li and Sr enrichment and SO4 depletion in the Carboniferous and Ordovician and K enrichment in part of the Ordovician relative to seawater. The relationship between δD and δ^18O shows that all the data of the waters decline towards the Global Meteoric Water Line with the intersection of them close to the present-day local meteoric water, suggesting that modern meteoric water has mixed with evaporated seawater. The ^87Sr/^86Sr ratios range from 0.7090 to 0.7011, significantly higher than those of the contemporary seawater. The δ^11B values range from ＋19.7 to ＋32.3‰, showing a decrease with the depth and B concentrations. The results suggest that isotopically distinct B and Sr were derived from external sources. However, since the percentages of illite are shown to increase with depth among clay minerals in the study area, i.e., illite is due to precipitation rather than leaching during deeper burial, it is unlikely for illite to have contributed a significant amount of B to the waters. Thus, B with low δ^11B values is interpreted to have been added mainly from thermal degradation of kerogen or the basalts in the Cambrian and Lower Ordovician.     

Groundwater flow dynamics in the complex aquifer system of Gidabo River Basin (Ethiopian Rift): a multi-proxy approach

Hydrochemical and isotope data in conjunction with hydraulic head and spring discharge observations were used to characterize the regional groundwater flow dynamics and the role of the tectonic setting in the Gidabo River Basin, Ethiopian Rift. Both groundwater levels and hydrochemical and isotopic data indicate groundwater flow from the major recharge area in the highland and escarpment into deep rift floor aquifers, suggesting a deep regional flow system can be distinguished from the shallow local aquifers. The δ¹⁸O and δ²H values of deep thermal (≥30 °C) groundwater are depleted relative to the shallow (<60 m below ground level) groundwater in the rift floor. Based on the δ¹⁸O values, the thermal groundwater is found to be recharged in the highland around 2,600 m a.s.l. and on average mixed with a proportion of 30 % shallow groundwater. While most groundwater samples display diluted solutions, δ¹³C data of dissolved inorganic carbon reveal that locally the thermal groundwater near fault zones is loaded with mantle CO₂, which enhances silicate weathering and leads to anomalously high total dissolved solids (2,000–2,320 mg/l) and fluoride concentrations (6–15 mg/l) exceeding the recommended guideline value. The faults are generally found to act as complex conduit leaky barrier systems favoring vertical mixing processes. Normal faults dipping to the west appear to facilitate movement of groundwater into deeper aquifers and towards the rift floor, whereas those dipping to the east tend to act as leaky barriers perpendicular to the fault but enable preferential flow parallel to the fault plane.     

A multi-isotope approach (O,H, C,S, B and Sr) to understand the source of water and solutes in some the thermal springs from West Coast geothermal area,India

The West Coast belt, consisting of nearly 60 thermal springs, is one of the most diversified geothermal fields in India. The present work describes the multi-isotopic (O, H, C, S, B and Sr) characterization of thermal waters carried out in the Tural-Rajwadi geothermal field, situated in southern sector of the west coast geothermal area. The aim of this study is to delineate the origin of thermal water as well as to ascertain the sources of carbon, sulphur, boron and strontium dissolved in those thermal springs. The stable isotopes (δ²H and δ¹⁸O) and tritium data indicate that these thermal springs are not recently recharged rain water rather, it contains very old component of water. Oxygen-18 shift is observed due to rock-water interaction over a long period of time. Carbon isotopic composition of DIC points out to the silicate weathering with soil CO₂ coming from C₃ type of plants whereas δ³⁴S of dissolved sulphate confirms the marine origin of sulphate. This marine signature is basically derived from paleo-seawater possibly entrapped within the flows. Boron isotopic data reveals that both the seawater and rock dissolution are the sources of boron in the thermal waters whereas high ⁸⁷Sr/⁸⁶Sr ratios (0.7220–0.7512) of the thermal waters conclusively establishes that archean granitic basement is the predominant rock source of strontium, not the Deccan flood basalts. In addition, like strontium, concentrations of lithium, rubidium and caesium are also governed by the rock-water interaction. Thus, the combined use of this multi-isotope technique coupled with trace element concentrations proves to be an effective tool to establish the sources of solutes in the thermal water.     

Conditions of the formation of thermomineral waters in the Talysh fold zone of the Lesser Caucasus (Azerbaijan) based on isotope-geochemical data (3Не/4Не, $${\delta ^{13}}{C_{c{o_2}}},{\delta ^{13}}{C_{c{h_4}}},{\delta ^{15}}{N_{{N_2}}}{,^{87}}Sr{/^{86}}Sr,\delta {D_{{H_2}O}},and{\delta ^{18}}{O_{{H_2}O}}$$)

It is shown that the gas and water phases of the thermal nitrogen–methane waters in the Talysh fold zone of the Lesser Caucasus mountain system contain helium and strontium with mantle isotope signatures (³Не/⁴Не from 200 × 10^–8 to 401 × 10^–8 and ⁸⁷Sr/⁸⁶Sr from 0.70490 to 0.70562). At the same time, clear signs of the mantle component in other gases (nitrogen, methane, and carbon dioxide) are absent. The δ¹⁵N value in nitrogen varies from +0.3 to +1.7‰, methane is mainly characterized by δ¹³C from–57.4 to–38.0‰, while δ¹³C(CО₂) varies from–24.4 to–11.3‰. An increase of the CО₂ content is accompanied by the decrease of δ¹³C in CО₂, against the background of increasing SO₄ content in the salt composition of waters. This indicates a microbial nature of CO₂ in the studied gases. Thus, the presence of mantle helium and strontium in the thermal waters is likely related to their leaching from the Pleogene–Neogene host volcanic rocks. The studies of the oxygen and hydrogen isotope composition in water revealed quite different mechanisms for the formation of cold and thermal waters of the region. The cold waters are mainly fed by local infiltration, whereas the feeding of thermal nitrogen–methane waters is strongly provided by transit atmogenic waters (>50%), which are formed in the mountain ranges at altitudes no less than 1600 m and spaced at 20–40 km or more from the thermal discharge sites.     

Assessment of mixing between shallow and thermal waters using geochemical and environmental isotope tracers (N Portugal): a review and reinterpretation

Caldas de Moledo thermal (27–46 °C) spring and borehole waters issue in the region of the famous Port Wine vineyards, in the Douro River valley (Northern Portugal). The most abundant lithotypes are lower Cambrian metasedimentary rocks, Variscan granitoids and aplite-pegmatitic veins. The thermal waters are characterised by pH ≈ 9.0, TDS ranging from 200 to 350 mg/L, and belong to the HCO₃–Na facies indicating that the reservoir rock should be mainly granite. Since the local Spa is strongly dependent on water quality, the effects of mixing between local shallow cold groundwaters and deep thermal waters have been properly investigated. In the SO₄ ^2? (mg/L) versus δ¹⁸O (‰ vs. V-SMOW) diagram we can observe that some of the thermal springs show evidences of mixing (higher SO₄ ^2? concentrations) with local meteoric waters infiltrated at lower altitude sites (enriched δ¹⁸O signatures), showing the “altitude effect” in the isotopic composition of the recharge waters. Similar trends can be found in the K⁺, NO₃ ^?, Ca²⁺ and Na⁺ (mg/L) versus δ¹⁸O (‰ vs. V-SMOW) diagrams. It should be stated that SO₄ ^2?, K⁺ and Ca²⁺ are present in the fertilizers and fungicides used in the vineyards in the northern part of the country. Up to now, the thermal waters from boreholes used in the local Spa do not show evidences of mixing with shallow groundwaters contaminated with agrochemicals. The results obtained so far indicate that in the near future, special attention should be put on the possible occurrence of diffuse agricultural contamination (related to the Port Wine vineyards) in the thermal spring waters.     

Chemistry,isotope values (δD, δ18O, δ34SSO4) and temperatures of the water inflows in two Gotthard tunnels,Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO₃ and Na–Ca–HCO₃ waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO₃ to Na–SO₄ waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO₄ composition. Calcium-Na–SO₄ waters are also present. They can be produced through interaction of either Na–HCO₃ waters with anhydrite or Ca–SO₄ waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO₃ waters are generated through interaction of Ca–HCO₃ waters with a local gneissic rock. The two main SO₄-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ³⁴S_SO4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ³⁴S_SO4 >∼+9‰ are controlled either by bacterial SO₄ reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.     

Hydrochemical characteristics of groundwater quality with special reference to fluoride concentration in parts of Mulugu-Venkatapur Mandals,Warangal district,Telangana

Hydrochemical studies were carried out in Mulugu-Venkatapur Mandals of Warangal district, Telangana state, India to find out the causes of high fluorides in groundwater and surface water causing a widespread incidence of fluorosis in local population. The fluoride concentration in groundwater ranges from 0.28 to 5.48 mg/l with a mean of 1.26 mg/l in pre-monsoon and 0.21 to 4.43 mg/l with a mean 1.45 mg/l in post-monsoon. About 32% and 34% of samples in pre and post-monsoon containing fluoride concentrations that exceed the permissible limit. The Modified Piper diagram reflects that, water belong to Ca⁺²-Mg⁺²-HCO₃ - to Na⁺-HCO₃ - facies. Negative chloroalkali indices in both the seasons prove that ion exchange took place between Na⁺ & K⁺ with Ca⁺² and Mg⁺² in aquatic solution in host rock. Different plots for major ions and molar ratios suggest that weathering of silicate rocks and water-rock interaction is responsible for major ion chemistry of water. High fluoride content in groundwater attributed to continuous water-rock interaction during the process of percolation with fluorite bearing country rocks under arid, low precipitation, and high evaporation conditions. The low calcium content in rocks and soils, and the presence of high content of sodium bicarbonate in soils and waters are important factors favouring high levels of fluoride in waters. The basement rocks provide abundant mineral sources of fluoride in the form of amphibole, biotite, fluorite, mica and apatite.     

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.     

Hydrogeochemistry and reservoir characterization of the Konya geothermal fields,Central Anatolia/Turkey

A conceptual model with water samples from ten geothermal fields (?smil, Ilg?n (Çavu?cugöl), Tuzlukçu-Ak?ehir, Seydi?ehir and Kavakköy, Hüyük, Ere?li-Akhüyük, Kad?nhan?, Cihanbeyli, Karap?nar and Bey?ehir) in the province of Konya defined the geothermal system. Carbonates, quartzite and marbles of Paleozoic metamorphics are the reservoir rocks and the heating sources are igneous rock intrusions and geothermal gradient. The variable thermal water (CaMgHCO₃, CaSO₄, NaSO₄, CaHCO₃, CaNaHCO₃, NaCl and CaNaClHCO₃) had EC and temperature between 177.8 and 56,100 μS/cm and between 18.3 and 44 °C, respectively. Ca²⁺ in geothermal fluids are associated with marble and carbonate rocks and the high chloride shows direct connection with deep geothermal system, and prolonged contact with evaporite rocks. Sulphate originates from dissolution of and oxidation of sulphate and sulphur-bearing minerals. The high As, B, F and Mn concentration in some thermal water samples were determined as 85 μg/l, 148.56 mg/l, 3.01 mg/l and 208.13 mg/l, respectively. Reservoir temperatures computed by Na/K geothermometers were between 85.37–158.89 °C for Ak?ehir thermal waters and 58.78–90.45 °C for Ere?li thermal waters. The maximum reservoir temperature of other geothermal waters was 75 °C by the silica geothermometers.     

Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.

Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70–120°C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are NaCaCl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H₂S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H₂S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl₄²⁻ and ZnCl₄²⁻, respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters.     

Geochemistry of mineral water and gases of the Razdolnoe Spa (Primorye,Far East of Russia)

New isotopic and chemical data on the sodium bicarbonate water and associated gases from the Razdolnoe Spa located in the coastal zone of Primorsky Kray of the Russian Far East, together with previous stable isotope data (δ¹⁸O, δD, δ¹³C), allow elucidation of the origin and evolution of the groundwater and gases from the spa. The water is characterized by low temperature (12 °C), TDS – 2.5–6.0 g/L, high contents of B (∼5 mg/L) and F (4.5 mg/L) and low contents of Cl and SO₄. Water isotopic composition indicates its essentially meteoric origin which may comply with an older groundwater that was recharged under different (colder) climatic conditions. Major components of bubbling gases are CH₄ (68 vol%), N₂ (28%) and CO₂ (4%). The obtained values δ¹³C and δD for CO₂ and CH₄ definitely indicate the marine microbial origin of methane. Thus the high methane content in the waters relates to the biochemical processes and presence of a dispersed organic matter in the host rocks. Based on the regional hydrogeology and the geological structure of the Razdolnoe Spa, Mesozoic fractured rocks containing Na–HCO₃ mineral water and gases are reservoir rocks, a chemical composition of water and gases originates in different environmental conditions.     

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.     

Major,trace element and stable isotope composition of water and muds precipitated from the hot springs of Bolivia: Are the waters of the spring's potential ore forming fluids?

The deposition of metal-rich black or reddish muds by many thermal springs in the Cordilleras and the Altiplano of Bolivia suggest that these geothermal waters may be related to those that once formed the world-class Bolivian tin, silver and gold mineralisation. The discharge temperatures of these springs are as high as 70 °C. According to δ¹⁸O, δD, tritium data and Ar/N₂ ratios these waters are predominantly of meteoric origin. Less than 10% of the discharging thermal water represents deep-seated metal-rich thermal brines of at least 530 °C according to carbon exchange between CO₂ and CH₄. These brines ascend along tectonic faults and mix with low-temperature meteoric water in surface-near aquifers. The meteoric component of the thermal water is recharged in the high Cordilleras with residence times exceeding 50 years. The chemical composition of the thermal water is dominated by the rather inefficient low-temperature leaching of the surface-near aquifer rocks by meteoric water. The small fraction of metal-rich hot deep-seated water is not able to increase the metal content of the water mix to a level sufficient to classify these thermal waters as ore-bearing. Surface-near leaching is supported, e.g., by the B/Li ratios of the spring water of the Western Cordillera and Caleras/Pulacayo in the Eastern Cordillera that correspond very closely to that of the easily leachable glassy inclusions of the outcropping andesitic lavas. The often remarkable metal content of the muds deposited by the springs originate from efficient scavenging of heavy metals by ferric oxyhydroxides. Under the given arid to semi-arid climate the muds are additionally enriched in metals by wind-transported dust. The present study does support a relation of the actual thermal waters with neither the classical subduction-related Upper Tertiary tin, silver and gold mineralisation nor the supposed younger Sb mineralisation of Bolivia.     

The origin of thermal waters in the northeastern part of the Eger Rift,Czech Republic

An investigation of the thermal waters in the Ústí nad Labem area in the northeastern part of the Eger Rift has been carried out, with the principal objective of determining their origin. Waters from geothermal reservoirs in the aquifers of the Bohemian Cretaceous Basin (BCB) from depths of 240 to 616 m are exploited here. For comparison, thermal waters of the adjacent Teplice Spa area were also incorporated into the study. Results based on water chemistry and isotopes indicate mixing of groundwater from aquifers of the BCB with groundwater derived from underlying crystalline rocks of the Erzgebirge Mts. Unlike thermal waters in Dě?ín, which are of Ca–HCO₃ type, there are two types of thermal waters in Ústí nad Labem, Na–HCO₃–Cl–SO₄ type with high TDS values and Na–Ca–HCO₃–SO₄ type with low TDS values. Carbon isotope data, speciation calculations, and inverse geochemical modeling suggest a significant input of endogenous CO₂ at Ústí nad Labem in the case of high TDS groundwaters. Besides CO₂ input, both silicate dissolution and cation exchange coupled with dissolution of carbonates may explain the origin of high TDS thermal waters equally well. This is a consequence of similar δ¹³C and ¹⁴C values in endogenous CO₂ and carbonates (both sources have ¹⁴C of 0 pmc, endogenous CO₂ δ¹³C around −3‰, carbonates in the range from −5‰ to +3‰ V-PDB). The source of Cl⁻ seems to be relict brine formed in Tertiary lakes, which infiltrated into the deep rift zone and is being flushed out. The difference between high and low TDS groundwaters in Ústí nad Labem is caused by location of the high mineralization groundwater wells in CO₂ emanation centers linked to channel-like conduits. This results in high dissolution rates of minerals and in different δ¹³C(DIC) and ¹⁴C(DIC) fingerprints. A combined δ³⁴S and δ¹⁸O study of dissolved SO₄ indicates multiple SO₄ sources, involving SO₄ from relict brines and oxidation of H₂S. The study clearly demonstrates potential problems encountered at sites with multiple sources of C, where several evolutionary groundwater scenarios are possible.     

Geochemical and isotope hydrological characterisation of geothermal resources at Godavari valley,India

Thermal waters at the Godavari valley geothermal field are located in the Khammam district of the Telangana state, India. The study area consists of several thermal water manifestations having temperature in the range 36–76 °C scattered over an area of ~35 km². The thermal waters are Na–HCO₃ type with moderate silica and TDS concentrations. In the present study, detailed geochemical (major and trace elements) and isotope hydrological investigations are carried out to understand the hydrogeochemical evolution of these thermal waters. Correlation analysis and principal component analysis (PCA) are performed to classify the thermal waters and to identify the different geochemical processes controlling the thermal water geochemistry. From correlation matrix, it is seen that TDS and EC of the thermal springs are mainly controlled by HCO₃ and Na ions. In PCA, thermal waters are grouped into two distinct clusters. One cluster represents thermal waters from deeper aquifer and other one from shallow aquifer. Lithium and boron concentrations are found to be similar followed by rubidium and caesium concentrations. Different ternary plots reveal rock–water interaction to be the dominant mechanism for controlling trace element concentrations. Stable isotopes (δ¹⁸O, δ²H) data indicate the meteoric origin of the thermal waters with no appreciable oxygen-18 shift. The low tritium values of the samples originating from deeper aquifer reveal the long residence time (>50 years) of the recharging waters. XRD results of the drill core samples show that quartz constitutes the major mineral phase, whereas kaolinite, dolomite, microcline, calcite, mica, etc. are present as minor constituents. Quartz geothermometer suggests a reservoir temperature of 100 ± 20 °C which is in good agreement with the values obtained from K–Mg and Mg-corrected K–Mg–Ca geothermometers.     

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius.Vesuvius groundwaters are dilute (mean TDS ∼ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. δD and δ¹⁸O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or ¹⁸O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO₂-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions.The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both ¹³C/¹²C and ³He/⁴He measurements indicate the contribution of a magmatic component with a δ¹³C ∼ 0‰ and R/R_a of ∼2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts.A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO₂ release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata-Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO₂ depleted, despite in some cases containing significant concentrations of magma-derived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.