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.     

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.     

Genesis and evolution of high-pCO2 groundwaters of the Mukhen spa (Russian Far East)

We present the chemical and isotope compositions of the water and gas phases of the unique Mukhen cold high-pCO₂ spa. Estimated 5¹⁸O, 5D, and 5¹³C_tic values and data on geology and hydrogeology of the studied area indicate that the source of the groundwaters is meteoric waters, whereas carbon dioxide is of deep genesis and numerous regional faults are gas-feeding channels. Calculations of equilibrium reactions in the water-rock system show that the upper-aquifer waters (HCO₃-Ca-Mg) with low TDS are undersaturated with carbonate minerals, montmorillonites, and aluminosilicates but are oversaturated with kaolinite, whereas the lower-aquifer waters (HCO3-Na) with high TDS are oversaturated with calcite, dolomite, and clay minerals but are undersaturated with main aluminosilicates. We propose a new concept of the formation of these groundwaters, demonstrating that long interaction between rocks and groundwaters in the presence of CO₂ and considerable precipitation of secondary minerals are responsible for the high TDS of the lower-aquifer waters (up to 14 g/L) and their geochemical type (HCO₃-Na) and unusual isotope composition (5¹⁸O = -25.2%c, 5D = -69.0%c).     

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.     

Conditions Of The Present-Day Hydrothermal Metamorphism Of Volcanic Rocks

Hydrothermal metamorphism in volcanic areas causes intense leaching of wall rocks with the development of secondary quartzites and rocks rich in alunite, dickite, and sericite. Three zones of different chemical activity, because of differences in P-T conditions, are evident: 1) zone of liquid hydrotherms (300m – 800m); 2) vaporization zone (10 m – 300m); and 3) condensation zone. Propylitization is common at greatest depth. In the vaporization zone, cooling and increase in pH lead to potassic metasomatism and development of zeolites and orthoclase. Argillization occurs at the surface. The change in the hot waters from acid solutions at depth to alkaline solutions at shallow depths is caused largely by vaporization of dissolved gases such as CO₂ and H₂S at lower pressures. Analyses of the deep circulating thermal waters in the Pauzhetka trough and of altered rocks in the discharge area are given as well as analyses of thermal waters and altered rocks in active volcanoes. Analyses of altered rocks from Wairakei are also compared.- -J. A. Redden.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

A geochemical and geophysical approach to derive a conceptual circulation model of CO2-rich mineral waters: A case study of Vilarelho da Raia, northern Portugal

The Vilarelho da Raia-Chaves region, located in northern Portugal adjacent to the Spanish border, is characterized by both hot and cold CO₂-rich mineral waters issuing from springs and drilled wells. The present paper updates the conceptual circulation model of the Vilarelho da Raia cold CO₂-rich mineral waters. Vilarelho da Raia mineral waters, dominated by Na and HCO₃ ions, have formed mainly by interaction with CO₂ of deep-seated mantle origin. The δ ¹⁸O, δ ²H and ³H values indicate that these waters are the result of meteoric waters infiltrating into Larouco Mountain, NW of Vilarelho da Raia, circulating at shallow depths in granitic rocks and moving into Vilarelho da Raia area. The conceptual geochemical and geophysical circulation model indicates that the hot and cold CO₂-rich mineral waters of Chaves (76 °C) and Vilarelho da Raia (17 °C) should be considered manifestations of similar but not the same geohydrological systems. Electronic Publication     

Arsenic-bearing carbonate waters: Geochemical and thermodynamic analysis of their genesis,transformation of arsenic migration species,and models for the genesis of hydrogenic as sulfide mineralization

Analysis of hydrogeochemical materials on As distribution in CO₂-bearing (carbonate) waters in various regions and the thermodynamic simulation of geochemical processes in rock-CO₂-bearing water systems made it possible to constrain the optimal conditions for As transfer from rocks into carbonate waters and the accumulation of this element in the waters. The problem was solved with regard for the various rates of As transitions from rocks to water: (a) high rates of As transitions from rocks in compliance with the ion exchange mechanism and (b) low rates of As transitions from rocks in compliance with the mechanism involving the decomposition of As-bearing minerals. Various mechanisms of As extraction from rocks result in the compositional diversity of the aqueous phase and various As migration species in CO₂-bearing waters, which, in turn, control the equilibrium concentration levels of this element. The principally important boundary conditions of As enrichment in CO₂-bearing waters are high \(P_{CO_2 } \) and R/W ratios in the geochemical systems, a preliminary increase in the Cl concentration in the CO₂-bearing waters, and the origin of these waters at high-density heat fluxes. As migration species were simulated for the model solutions and real carbonate waters of various geochemical types, and it is demonstrated that the predominant As species are oxygen-bearing HAsO ₂ ⁰ , and AsO ₂ ^? at a subordinate role of the sulfide HAs₂S ₄ ^2? , and As₂S ₄ ^2? — species even at high Σ S^2? in the system. Two models of the genesis of solid As sulfides in CO₂-bearing waters are analyzed: (1) with oxygen-bearing species (HAsO ₂ ⁰ , and AsO ₂ ^? ), which occur most widely, and (2) with sulfide species (As₂S ₄ ^2? , HAs₂S ₄ ^? , and As₄S ₇ ^2? ), which occur not as widely.     

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).     

Major ion chemistry of groundwater from perched-water bodies of the Azores (Portugal) volcanic archipelago

A dataset of major ion composition of 246 samples from cold-water springs discharging from perched-water bodies at volcanic islands (Azores archipelago, Portugal) reveal waters with low mineralization, which evolve due to two main geochemical processes: (1) seawater spraying and (2) dissolution of primary minerals of volcanic rocks. As a result, water facies range from Na–Cl to Na–HCO₃ type waters. The relationship between alkali, alkali–earth metals and HCO₃⁻ shows differences between waters discharging from perched-water bodies in basaltic rocks comparing to more evolved rocks of trachytic nature. The use of principal component analysis shows that water-rock interaction is limited, which is compatible with the geochemical observations and with the hydrogeological environment.     

Input of Sr/Sr ratios and Sr geochemical signatures to update knowledge on thermal and mineral waters flow paths in fractured rocks (N-Portugal)

Strontium isotopes and other geochemical signatures are used to determine the relationships between CO₂-rich thermal (Chaves: 76 °C) and mineral (Vilarelho da Raia, Vidago and Pedras Salgadas: 17 °C) waters discharging along one of the major NNE–SSW trending faults in the northern part of mainland Portugal. The regional geology consists of Hercynian granites (syn-tectonic-310 Ma and post-tectonic-290 Ma) intruding Silurian metasediments (quartzites, phyllites and carbonaceous slates). Thermal and mineral waters have ⁸⁷Sr/⁸⁶Sr isotopic ratios between 0.716713 and 0.728035. ⁸⁷Sr/⁸⁶Sr vs. 1/Sr define three end-members (Vilarelho da Raia/Chaves, Vidago and Pedras Salgadas thermal and mineral waters) trending from rainfall composition towards that of the CO₂-rich thermal and mineral waters, indicating different underground flow paths. Local granitic rocks have ⁸⁷Sr/⁸⁶Sr ratios of 0.735697–0.789683. There is no indication that equilibrium was reached between the CO₂-rich thermal and mineral waters and the granitic rocks. The mean ⁸⁷Sr/⁸⁶Sr ratio of the thermal and mineral waters (0.722419) is similar to the Sr isotopic ratios of the plagioclases of the granitic rocks (0.71261–0.72087). The spatial distribution of Sr isotope and geochemical signatures of waters and the host rocks suggests that the thermal and mineral waters circulate in similar but not the same hydrogeological system. Results from this study could be used to evaluate the applicability of this isotope approach in other hydrogeologic investigations.     

Lithium in spilites

During spilitisation the abundance of Li increases from about 12 ppm in normal basaltic rocks to an average of 75 ppm, with some spilites containing up to 190 ppm. This is relatively far greater than the increase of <50% in Na. Also the ratio CaO/Al₂O₃ decreases from about 1.0 to <0.1 and the H₂O content increases markedly.Alteration of this kind requires waters rich in both Na and Li, with the material added having a ratio 10⁵ Li/Na of about 750: the ratio for seawater is 1.8 but most subsurface waters have higher ratios and are more likely agents of spilitisation.Volcanic hydrothermal brines have suitable Li and Na abundances and are known to have reacted with fresh basalts to produce spilitic alteration: in cases of spilitisation of volcanogenic sediments, reaction with non-volcanic brines may have occurred. In both cases the waters must initially have high CO₂ and low Ca activities.     

The role of vertical migration of high-temperature fluids in the genesis of formation waters in oil-gas fields in the north of the Western Siberian basin

All northern areas of Western Siberia exhibit a discontinuity in the normal vertical hydrochemical zoning and formation of an inversion hydrochemcial profile characterized by total mineralization of formation waters that decrease with depth and by the discovery of waters with mineralization levels of 1–7 g/L and less, as well as a simultaneous “inconsistent” change in the chemical composition of formation waters with Cl-Na-Ca to HCO₃-Cl-Na deeper than 2–3 km and simultaneous “irregular’ change in the chemical composition of formation waters with Cl-Na-Ca to HCO₃-Cl-Na. Based on the use of the B/Br ratio and a Na-K geothermometer, a conclusion is made that the formation of slightly (<5 g/L) mineralized hydrocarbonate-sodium waters is caused by seepage of a considerable amount of deep high-temperature (>150°C) fluids saturated with CO₂ into water-bearing rocks. This indicates the formation of deposits of hydrocarbons that are found in the regions of inversion waters as result of the upward vertical, but not lateral formation migration of a water-oil mixture.     

The isotopic and chemical composition of CO2-rich thermal waters in the Mont-Dore region (Massif-Central,France)

Chemical and isotope compositions of fluid samples, collected between 1974 and 1986 from 52 springs or shallow boreholes located in the Mont-Dore region (Massif Central, France), were examined. Some springs and wells were sampled several times during this period. The fluids emerge from Quaternary volcanic rocks or Paleozoic granite at temperatures between 4 and 62°C, and the origin of the H₂O is meteoric. The waters can be classified into three groups: bicarbonate fluids, mixed bicarbonate-chloride fluids (with a mineralization up to 8 g/l), and acid-sulfate fluids. Only two fluids contain sufficient Cl⁻ to be considered as ‘mature’ waters. Previous work has demonstrated that they all contain partly mantle-derived CO₂ gas, and that the CO₂-rich gas phase and bicarbonate-chloride waters are separated at substantial depth.Mineralized fluids circulate at depth and undergo several processes, such as cooling or dilution with recent freshwater, during their ascent to the surface. Therefore, the CO₂-rich gas phase can be partly dissolved in the freshwater, or in deep fluids after their dilution. This process leads to the dissolution of surrounding rocks; such dissolution is discussed on the basis of major-element concentrations (Na, K, Ca, Mg), as well as the Sr 87/86 isotope ratio. Dissolution of S-bearing minerals has also been demonstrated. The presence of the CO₂-rich gas phase also leads to isotope exchange between CO₂ and H₂O. Some mineralized fluids are less affected by these processes than others, in which case they display the chemical and isotopic characteristics of the original deep fluids.It was shown that the applicability of geothermometer calculations for these waters is hampered by several processes that modify the chemical composition. However, some geothermometers can be used for estimating the temperature of the deep fluids using the chemical composition of the less modified fluids. They indicate that fluids emerging from volcanic rocks in the Dordogne valley reach temperatures of around 100–130°C at depth, while the temperature of the fluid that issues from the granite at Saint-Nectaire is 160–175°C at depth.     

Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano,Italy

This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and ⁸⁷Sr/⁸⁶Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and ⁸⁷Sr/⁸⁶Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water–rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average ⁸⁷Sr/⁸⁶Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704–0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher ⁸⁷Sr/⁸⁶Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO₄ and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites).     

Hydrogeochemical properties of CO2-rich thermal–mineral waters in Kayseri (Central Anatolia), Turkey

The present study highlights the hydrogeological and hydrogeochemical characteristics of the CO₂-rich thermal–mineral waters in Kayseri, Turkey. These waters of Dokuzpınar cold spring (DPS) (12–13°C), Yeşilhisar mineral spring (YMS) (13–16°C), Acısu mineral spring (ACMS) (20–22.5°C), Tekgöz thermal spring (TGS) (40–41°C), and Bayramhacı thermal-mineral spring (BTMS) (45–46.5°C) have different physical and chemical compositions. The waters are located within the Erciyes basin in the Central Anatolian Crystalline complex consisting of three main rock units. Metamorphic/crystalline rocks occur as the basement, sedimentary rocks of Upper Cretaceous-Quaternary age form the cover, and volcanosedimentary rocks Miocene-Quaternary in age represent the extrusive products of magmatism acting in that period. All these units are covered unconformably by terrace and alluvial deposits, and travertine occurrences have variable permeability. Dokuzpinar cold spring, YMS and ACMS localized mainly along the faults within the region have higher Na⁺ and Cl⁻ contents whereas TGS and BTMS have higher amounts of Ca²⁺ and HCO ₃ ⁻ . The high concentrations of Ca²⁺ and HCO ₃ ⁻ are mainly related to the high CO₂ contents resulting from interactions with carbonate rocks. Whereas the high Na⁺ content is derived from the alkaline rocks, such as syenite, tuff and basalts, the Cl⁻ is generally connected to the dissolution of the evaporitic sequences. These waters are of meteoric-type. BTMS deviates from meteoric water line. The content is related to the increases in the δ¹⁸O compositions due to mineral–water interaction (re-equilibrium) process. CO₂-dominated YMS and ACMS with low temperatures have higher mineralizations. Yeşilhisar mineral spring, ACMS, TGS and BTMS are oversaturated in terms of calcite, aragonite, dolomite, goethite and hematite, and undersaturated with respect to gypsum, halite and anhydrite. Yeşilhisar mineral spring, ACMS and BTMS are also characterized by recent travertine precipitation. Dokuzpınar cold spring is undersaturated in terms of the above minerals. The higher ratios of Ca/Mg and Cl/HCO₃, and lower ratios of SO₄/Cl in BTMS than TGS suggest that TGS has shallow circulation compared to BTMS, and/or has much more heat-loss enroute the surface. The sequence of hydrogeochemical and isotopic compositions of the waters is in an order of DPS>YMS>ACMS>TGS>BTMS and this suggests a transition period from a shallow circulation to a deep circulation path.     

Rare earth elements,neodymium and strontium isotopic systematics in mineral waters: evidence from the Massif Central,France

Rare Earth Elements (REEs), and Sr and Nd isotope distributions, have been studied in mineralized waters from the Massif Central (France). The CO₂-rich springs are characterized by a neutral pH (6–7) associated with total dissolved solids (TDS) from 1 to 7 g l⁻¹. The waters result from the mixing of very mineralized water pools, thought to have equilibrated at a temperature of around 200°C with superficial waters. These two mineral water pools evidenced by Sr isotopes and dissolved REEs could reflect 2 different stages of water–rock interaction and an equilibrium with different mineral assemblages.The concentrations of individual dissolved REEs and total dissolved REEs (ΣREE), in the mineral waters examined, vary over several orders of magnitude but are not dependent on the main parameters of the waters (TDS, T°C, pH, Total Organic C). The dissolved REE concentrations presented as upper continental crust normalized patterns show HREE enrichment in most of the samples. The time evolution of REE patterns does not show significant fluctuations except in 1 borehole, located in the Limagne d’Allier area, which was sampled on 16 occasions over an 18 month period. Ten samples are HREE-enriched, whereas 6 samples show flat patterns.The aqueous speciation of REEs shows that CO²⁻₃ complexes dominate (>80%) over the free metal, F⁻, SO²⁻₄ and HCO⁻₃ complexes. The detailed speciation demonstrates that the fractionation of REEs (i.e. the HREE enrichment) in CO₂-rich and pH neutral fluids is due essentially to the predominance of the CO²⁻₃ complexes.The Sr isotopic composition of the mineral waters in the Massif Central shows different mixing processes; in the Cézallier area at least 3 end-member water types exist. The most dilute end-member is likely to originate as poorly mineralized waters with minimal groundwater circulation. Two other mineralized end-members are identified, although the link between the geographical location of spring outflow and the mixing proportion between the 2 end-members is not systematic. The range in ϵ_Nd(0) for mineralized waters in the Massif Central correlates well with that of the known parent rocks except for 4 springs. One way to explain the ϵ_Nd(0) in these instances is a contribution from drainage of volcanic rocks. The isotopic systematics help to constrain the hydrogeological models for this area.     

Halogens in water from the crystalline basement of the Gotthard rail base tunnel (central Alps)

Drilling of the new Gotthard rail base tunnel (central Alps) opened a large number of water-conducting fractures in granite and gneiss of the crystalline basement. The overburden reaches locally more than 2000 m and water and rock temperature is up to 45 °C. The tunnel crosses a series of steeply dipping fractured rock units that also crop out at the surface above the tunnel. Recharge water enters the fractured rocks in the high mountainous area, migrates gravity driven to the sampling locality in the tunnel. Along its flow path it reacts with rocks exposed on the fractures where it dissolves the principal granite minerals, resulting in high-pH Na₂CO₃ waters.The tunnel waters contain unusually high concentrations of fluoride ranging from 5 to 29 mg/L. Alteration of F-bearing biotite to F-free chlorite is one of the sources of fluorine. The highest F-concentrations result from the equilibration of low-Ca waters with fluorite. Fluoride concentration is strongly lithology-dependent and sharp discontinuities in both, concentration and saturation state with respect to fluorite occur at the contacts of the different gneiss and granite slabs.Chloride concentrations vary between 1 and 1300 mg/L. In contrast, the Cl/Br mass ratio exhibits small variations and centers around 110 suggesting a common source for the Cl and Br, which is independent of the lithology. In the northern part of the tunnel, Cl and Br are chiefly derived from saline pore fluids of one lithology which is then mixed with low-salinity water along flow paths. Cl/Br ratios of the waters in the southern part of the tunnel section are similar to those measured in experimental leachates from different tunnel rocks, suggesting that leaching of metamorphic fluids in the pore space is the main source of both Cl and Br.     

Meteoric water-basalt interactions. II: A field study in N.E. Iceland

The compositions of rain, snow, melt, spring and geothermal waters from the rift zone of N.E. Iceland can be explained by seaspray addition, chemical fractionation at the seawater-air interface, burning of fossil fuel, farming activities, purification by partial melting of snow and ice, dissolution of basalts and buffering by alteration minerals. The dissolution of the rocks appears to be incongruent. During solute acquisition, spring compositions move through the stability fields of kaolinite and smectite to the laumontite and illite fields. All but four of the springs are undersaturated with respect to calcite. Silica concentrations are compatible with the solubility of basaltic glass. The reactions reflected in the spring waters appear to have taken place sealed off from atmospheric CO₂ after initial saturation.The geothermal waters which are recharged by the spring waters are depleted in Mg and Ca but enriched in carbon and sulfur with respect to dissolution of primary rocks. Expressions are derived relating dissolution rates of rocks, age of groundwaters, physical properties of groundwaters and mass transfer. The characteristic rock particle radii in the cold water aquifers range from 0.2 to 2 cm and the characteristic crack openings are of the order 0.04 to 0.4 cm. Using laboratory studies on the Icelandic lavas as a guide, the residence times of the cold waters in the aquifers can be estimated at 60 days to 4 years. The average active surface area of the aquifers enclosing 1000 g of spring water is of the order of 0.6 to 6 m² and these 1000 g of water have reacted with 0.1 to 1 g of basaltic rocks. The same mass of thermal water has interacted with 100 to 300 g of unaltered rocks.     

Geochemistry and origin of saline groundwaters in the Fennoscandian Shield

Chemical and isotopic analyses of water from drill holes and mines throughout the Fennoscandian Shield show that distinct layers of groundwater are present. An upper layer of fresh groundwater is underlain by several sharply differentiated saline layers, which may differ in salinity, relative abundance of solutes, and O, H, Sr and S isotope signature. Saline groundwater can be classified into four major groups based on geochemistry and presumed origin. Brackish and saline waters from 50–200 m depth in coastal areas around the Baltic Sea exhibit distinct marine chemical and isotopic fingerprints, modified by reactions with host rocks. These waters represent relict Holocene seawater. Inland, three types of saline groundwater are observed: an uppermost layer of brackish and saline water from 300–900 m depth; saline water and brines from 1000–2000 m depth; and superdeep brines which have been observed to a depth of at least 11 km in the drill hole on the Kola Peninsula, U.S.S.R. Electrical and seismic studies in shield areas suggest that such brines are commonly present at even greater depths. The salinity of all inland groundwaters is attributed predominantly to water-rock interaction. The main solutes are Cl, Ca, Na and Mg in varying proportions, depending on the host rock lithology. The abundance of dissolved gases increases with depth but varies from site to site. The main gas components are N₂, CH₄ (up to 87 vol.%) and locally H₂. The δ¹³C value for methane is highly variable (−25 to −46%), and it is suggested that hydrothermal or metamorphic gases trapped within the surrounding rocks are the most obvious source of CH₄. The uppermost saline water has meteoric oxygen-hydrogen isotopic compositions, whereas values from deeper water plot above the meteoric water line, indicating considerably longer mean residence time and effective low temperature equilibration with host rocks. Geochemical and isotopic results from some localities demonstrate that the upper saline water cannot have been formed through simple mixing between fresh water and deep brines but rather is of independent origin. The source of water itself has not been satisfactorily verified although superdeep brines at least may contain a significant proportion of relict Precambrian hydrothermal or metamorphic fluids.