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 impact of water-rock interaction and vegetation on calcium isotope fractionation in soil- and stream waters of a small, forested catchment (the Strengbach case)

This study aims to constrain the factors controlling the calcium isotopic compositions in surface waters, especially the respective role of vegetation and water-rock interactions on Ca isotope fractionation in a continental forested ecosystem. The approach is to follow changes in space and time of the isotopic composition and concentration of Ca along its pathway through the hydro-geochemical reservoirs from atmospheric deposits to the outlet of the watershed via throughfalls, percolating soil solutions and springs. The study is focused on the Strengbach catchment, a small forested watershed located in the northeast of France in the Vosges mountains. The δ^44/40Ca values of springs, brooks and stream waters from the catchment are comparable to those of continental rivers and fluctuate between 0.17 and 0.87‰. Soil solutions, however, are significantly depleted in lighter isotopes (δ^44/40Ca: 1.00-1.47‰), whereas vegetation is strongly enriched (δ^44/40Ca: −0.48‰ to +0.19‰). These results highlight that vegetation is a major factor controlling the calcium isotopic composition of soil solutions, with depletion in “light” calcium in the soil solutions from deeper parts of the soil compartments due to preferential ⁴⁰Ca uptake by the plants rootsystem. However, mass balance calculations require the contribution of an additional Ca flux into the soil solutions most probably associated with water-rock interactions. The stream waters are marked by a seasonal variation of their δ^44/40Ca, with low δ^44/40Ca in winter and high δ^44/40Ca in spring, summer and autumn. For some springs, nourishing the streamlet, a decrease of the δ^44/40Ca value is observed when the discharge of the spring increases, with, in addition, a clear covariation between the δ^44/40Ca and corresponding H₄SiO₄ concentrations: high δ^44/40Ca values and low H₄SiO₄ concentrations at high discharge; low δ^44/40Ca values and high H₄SiO₄ concentrations at low discharge. These data imply that during dry periods and low water flow rate the source waters carry a Ca isotopic signature from alteration of soil minerals, whereas during wet periods and high flow rates admixture of significant quantities of ⁴⁰Ca depleted waters (vegetation induced signal) from uppermost soil horizons controls the isotopic composition of the source waters. This study clearly emphasizes the potential of Ca isotopes as tracers of biogeochemical processes at the water-rock-vegetation interface in a small forested catchment.     

Hydrogeochemistry and stable isotopes of thermal springs: earthquake-related chemical changes along Belice Fault (Western Sicily)

Three geothermal systems, Montevago, Castellammare-Alcamo and Sciacca, are located along the main seismogenetic structures in Western Sicily. Concentrations of dissolved species including the gases CO₂, N₂, He and the results of stable isotope measurements δ¹⁸O, δD and δ¹³C_TDIC in water samples collected from six thermal springs and 28 cold discharges were used to characterise their feeder aquifers and to reveal the relationships between water chemistry and regional seismicity. The Sciacca thermal springs differ chemically and isotopically from those of Montevago and the Castellammare-Alcamo areas. The inferred deep end-members of the thermal waters of Montevago and Castellammare-Alcamo are almost similar, suggesting that both systems are fed by carbonate waters and selenite waters. A slight contribution (1–3%) of seawater, during groundwater ascent it is also present. The Sciacca thermal springs are fed by a deep reservoir comprising a mixture of 50% carbonate water and 50% seawater. During ascent towards the surface, these waters interact with NaCl-rich evaporite layers. By combination of published and present data significant temporal variations of temperature and some chemical parameters in the thermal waters of Western Sicily have been recorded. These variations were mostly between 1966 and 1969. Although the data are discontinuous it is still possible to reveal a direct link between physico–chemical changes in the Acqua Pia and Terme Selinuntine springs and the 1968 Belice Valley earthquake. Within the studied springs, two kinds of geochemical behaviour have been recognised. The chemistry of the Montevago thermal springs was permanently changed in response to changes in the groundwater system. Water temperature and dissolved SO₄, Cl, Na, and TDS showed minimum values before the earthquake and maximum values after the event. Almost constant values substantially higher than before, were recorded after the seismic event. Conversely, the temporal variations observed in the waters of the Terme Selinuntine spring, from 1965 to 1991, exhibit a transient increase most probably caused by a temporary contribution of deep CO₂-rich fluids caused by the strain release during the 1968 earthquake.     

Isotopic composition of thermal waters in Chukotka

Twenty three groups of thermomineral springs in eastern Chukotka with the discharge temperature of 2 to 97°C and mineralization of 1.47 to 37.14 g/l are studied and compared with surface freshwater from their localities. The δD and δ¹⁸O values in surface waters vary from ?121.4 to ?89.5‰ and from ?16.4 to ?11.1‰, respectively, while respective values in thermomineral waters range from ?134.2 to ?92.5‰ and from ?17.6 to ?10.5‰. The δD value in surface waters decreases from the east to west, i.e., toward interior areas of the peninsula. Hydrothermal springs most depleted in deuterium (δD < ?120‰) are localized in the geodynamically active Kolyuchinskaya-Mechigmen Depression. According to the proposed formation model of Chukotka thermomineral waters, their observed chemical and isotopic characteristics could result from the mixing (in different proportions) of surface waters with the deep-sourced isotopically light mineralized component (δD ≈ ?138‰, δ¹⁸O ≈ ?19‰, M = 9.5?14.7 g/l). The latter originates most likely from subpermafrost waters subjected to slight cryogenic metamorphism.     

Chemical and isotopic characteristics and origin of spring waters in the Lanping–Simao Basin,Yunnan, Southwestern China

The chemical and isotopic characteristics (oxygen, hydrogen, and strontium) of spring waters and isotopic compositions of helium (He) and neon (Ne) in gases escaping from spring waters in the Lanping–Simao Basin are studied. A total of twenty-one spring water samples (twelve hot springs, four cold springs, and five saline springs) and eleven gas samples were collected from the study area, including one spring and one gas sample from northern Laos. It is found that saline spring waters in the study area are of chloride type, cold spring waters are of carbonate type or sulfate type, and hot spring waters are of various types. High total dissolved solids levels in saline springs are significantly related to Upper Cretaceous–Paleocene salt-bearing strata. On the basis of hydrochemical geothermometry, the reservoir temperatures (T_r) for hot springs, cold springs, and saline springs are 65.5–144.1, 37.8–64.4, and 65.1–109.0 °C, respectively, and the circulation depths of saline springs are much larger than those of hot and cold springs. The oxygen and hydrogen isotopic compositions of springs in the Lanping–Simao Basin and northern Laos are primarily controlled by meteoric waters with obvious latitude and altitude effects, and are also influenced by δ¹⁸O exchange to some extent. Most Sr²⁺ in spring waters of the study area is derived from varied sources (carbonate, evaporite, and silicate mineral dissolution), and the Sr isotopic compositions are greatly influenced by volcanic rocks. Wide distribution of crust-derived He in the Lanping–Simao Basin and northern Laos reveal that faults in these areas may not descend to the upper mantle. It is concluded that water circulation in the study area may be limited above the upper mantle, while saline springs may originate from the Upper Cretaceous–Paleocene evaporites. Hydrochemical characteristics demonstrate affinities among the Lanping–Simao Basin, northern Laos, and Yanjing, eastern Tibet, while disaffinities are observed between these areas and Tengchong on the basis of the hydrochemical characteristics and noble gas isotopic compositions.     

Coseismic geochemical variations in some gas emissions of Umbria region (Central Italy)

Coseismic geochemical variations have been detected in some gaseous vents and natural springs during the last seismic crisis occurred in Umbria region (Central Apennines), that started on September 26^th, 1997 with several moderate earthquakes (up to M1 5.8). The results of chemical analyses performed on both gas and water samples taken at a weekly rate, combined with analyses on continuous gas flow rate nearby San Faustino site, suggest that the variations can be interpreted as possible consequence of the crustal permeability changes induced by earthquake shaking.     

Geochemistry of thermal springs,Alhama de Granada (southern Spain)

The waters of the thermal springs at Alhama de Granada vary in temperature between 27 and 45°C. Temporal changes in the composition of the principal spring (Baños Viejos) indicate that a small degree of mixing may occur between deep thermal waters and shallow groundwater. Slight compositional variations also occur between the various thermal springs in the study area. These spatial variations are due to the different local hydrodynamic conditions in the springs. Towards the north in less hydraulically transmissive rocks, cooling of the rising water is more noticeable, as are ion exchange and processes of SO₄ reduction. The chemical composition of the water is related to the dissolution of evaporites (SO₄ and Cl salts), carbonates and silicates, and to the possible existence of sources of S within the rock. Estimates of the mean residence times have been obtained based on ¹⁴C_DIC and T. The state of thermodynamic equilibrium at the spring discharge was calculated using the SOLMINEQ.88 program. The results indicate that all the samples are supersaturated with respect to quartz, chalcedony, cristobalite, calcite, aragonite and dolomite, and undersaturated with respect to gypsum, anhydrite and halite. The use of different geothermometers and modelling of saturation indices for quartz, albite and anhydrite indicate temperatures of about 110°C.     

Hydrochemistry and environmental isotopes of spring water and their relation to structure and lithology identified with remote sensing methods in Wadi Araba,Egypt

Springs located at the historical sites of Wadi Araba (Eastern Desert of Egypt) and emerging from the escarpments of the Northern and Southern Galala Plateaus were investigated. A combination of methods, including hydrochemistry, stable and radioisotope composition, and structural analyses based on satellite data, provided information about the structure of the subsurface and the derived groundwater flow paths. Satellite images reveal karst features within the northern plateau, e.g. conical landforms. Karstic caves were documented along both escarpments. Chemical analysis of floodwater from Wadi Araba indicates higher concentrations of terrestrial salts compared to floodwaters from central and southern parts of the desert. δ¹⁸O and δ²H signatures in spring waters resemble those of floodwater and fall on the global meteoric water line, confirming their fast infiltration with minor influence of evaporation. The aquifer feeding the springs of the Northern Galala Plateau has low retention and the springs dry out quickly, even after heavy rainfall. Contrastingly, ³H activities in springs emerging from the Southern Galala Plateau refer to much slower subsurface passage. With respect to ³H content (3.8 TU) in recent flood waters, the spring water at Southern Galala Plateau contains about 40% recently recharged groundwater. However, its largest spring—the St. Antony spring—discharges water with a radiocarbon age of about 15,000 years. In combination with this spring’s constant and high discharge over a period of several months, that age estimate suggests a large reservoir with moderate to high retention.

     

Mixing processes in hydrothermal spring systems and implications for interpreting geochemical data: a case study in the Cappadocia region of Turkey

Mixing is a dominant hydrogeological process in the hydrothermal spring system in the Cappadocia region of Turkey. All springs emerge along faults, which have the potential to transmit waters rapidly from great depths. However, mixing with shallow meteoric waters within the flow system results in uncertainty in the interpretation of geochemical results. The chemical compositions of cold and warm springs and geothermal waters are varied, but overall there is a trend from Ca–HCO₃ dominated to Na–Cl dominated. There is little difference in the seasonal ionic compositions of the hot springs, suggesting the waters are sourced from a well-mixed reservoir. Based on δ¹⁸O and δ²H concentrations, all waters are of meteoric origin with evidence of temperature equilibration with carbonate rocks and evaporation. Seasonal isotopic variability indicates that only a small proportion of late spring and summer precipitation forms recharge and that fresh meteoric waters move rapidly into the flow system and mix with thermal waters at depth. ³H and percent modern carbon (pmC) values reflect progressively longer groundwater pathways from cold to geothermal waters; however, mixing processes and the very high dissolved inorganic carbon (DIC) of the water samples preclude the use of either isotope to gain any insight on actual groundwater ages.     

Hydrogeochemical and isotopic characteristics of the Ilica geothermal system (Erzurum,Turkey)

In this paper, the hydrochemical isotopic characteristics of samples collected from geothermal springs in the Ilica geothermal field, Eastern Anatolia of Turkey, are examined and described. Low-temperature geothermal system of Ilica (Erzurum, Turkey) located along the Eastern Anatolian fault zone was investigated for hydrogeochemical and isotopic characteristics. The study of ionic and isotopic contents shows that the thermal water of Ilica is mainly, locally fed by groundwater, which changes chemically and isotopically during its circulation within the major fault zone reaching depths. The thermal spring has a temperature of 29–39 °C, with electrical conductivity ranging from 4,000 to 7,510 µS/cm and the thermal water is of Na–HCO₃–Cl water type. The chemical geothermometers applied in the Ilica geothermal waters yielded a maximum reservoir temperature of 142 °C according to the silica geothermometers. The thermal waters are undersaturated with respect to gypsum, anhydrite and halite, and oversaturated with respect to dolomite. The dolomite mineral possibly caused scaling when obtaining the thermal waters in the study area. According to the enthalpy chloride-mixing model, cold water to the thermal water-mixing ratio is changing between 69.8 and 75 %. The δ¹⁸O–δ²H compositions obviously indicate meteoric origin of the waters. Thermal water springs derived from continental precipitation falling on to higher elevations in the study area. The δ¹³C ratio for dissolved inorganic carbonate in the waters lies between 4.63 and 6.48 ‰. In low-temperature waters carbon is considered as originating from volcanic (mantle) CO₂.     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.     

Isotope–geochemical characterization and geothermometrical modeling of Uttarakhand geothermal field,India

Uttarakhand geothermal area, located in the central belt of the Himalayan geothermal province, is one of the important high temperature geothermal fields in India. In this study, the chemical characteristics of the thermal waters are investigated to identify the main geochemical processes affecting the composition of thermal waters during its ascent toward the surface as well as to determine the subsurface temperature of the feeding reservoir. The thermal waters are mainly Ca–Mg–HCO₃ type with moderate silica and TDS concentrations. Mineral saturation states calculated from PHREEQC geochemical code indicate that thermal waters are supersaturated with respect to calcite, dolomite, aragonite, chalcedony, quartz (SI > 0), and undersaturated with respect to gypsum, anhydrite, and amorphous silica (SI < 0). XRD study of the spring deposit samples fairly corroborates the predicted mineral saturation state of the thermal waters. Stable isotopes (δ¹⁸O, δ²H) data confirm the meteoric origin of the thermal waters with no oxygen-18 shift. The mixing phenomenon between thermal water with shallow ground water is substantiated using tritium (³H) and chemical data. The extent of dilution is quantified using tritium content of thermal springs and non-thermal waters. Classical geothermometers, mixing model, and multicomponent fluid geothermometry modeling (GeoT) have been applied to estimate the subsurface reservoir temperature. Among different classical geothermometers, only quartz geothermometer provide somewhat reliable estimation (96–140 °C) of the reservoir temperature. GeoT modeling results suggest that thermal waters have attained simultaneous equilibrium with respect to minerals like calcite, quartz, chalcedony, brucite, tridymite, cristobalite, talc, at the temperature 130 ± 5 °C which is in good agreement with the result obtained from the mixing model.     

Hydrogeochemical and isotopic composition of a low-temperature geothermal source in northwest Turkey: case study of Kirkgecit geothermal area

Chemical and isotopic compositions of three hot springs and one cold spring in the Kirkgecit geothermal field, located 15 km southwest of Canakkale-Biga in the northwest of Turkey, were monitored five times during 2005 and 2007. The physico-chemical characteristics of the hot springs are average discharge 3–3.5 L/s, surface temperature 45–52°C, pH 8.9–9.3, and electrical conductivity (EC) 620–698 μS/cm. The cold spring has a temperature of 12–13°C, pH 7.5–8.3, and EC 653–675 μS/cm. The hot waters are Na-SO₄ type, whereas the cold water is Ca-HCO₃ type. Chemical geothermometers suggest that the reservoir temperature is around 80–100°C. The isotopic data (oxygen-18, deuterium and tritium) indicate that the thermal waters are formed by local recharge and deep circulation of meteoric waters.     

Seasonal variation in nature and chemical compositions of spring water in Cuihua Mountain,Shaanxi Province,central China

Two springs (Cuihua Spring, Shuiqiuchi Spring) in Cuihua Mountain of the Qinling Mountains were observed and sampled monthly during 2004 and 2005 to trace their physical properties and chemical compositions with seasons. Although both pH values and cation (Ca²⁺, Mg²⁺, K⁺, and Na⁺) contents of Cuihua Spring are higher than those of Shuiqiuchi Spring, seasonal variations in both springs are obvious. The pH values of both spring waters are between 5.69 and 6.98, lower than that of rainwater during summer and autumn. From January to November, the pH values of both springs similarly vary from high to low and then to high again. Variations in electric conductivities of two spring waters are contrary, although their electric conductivities are positively correlative with the cation content respectively. This can be attributed to different water sources of the two springs or different acidic rocks they passed. The contents of HCO₃ ⁻, Ca²⁺, Mg²⁺, K⁺, and Na⁺ are low, indicating a low silicate weathering that the strata in this district are mainly composed of granite and schist of quartz and mica. Differing from change in spring water in karst regions of South China where abundant precipitation and dilution of rainwater cause low pH and electric conductivity in summer and autumn, the seasonal variations in the pH values and the electric conductivities of two springs in Qinling Mountains are attributed to seasonal changes in CO₂ produced by microorganisms’ activity in soil within respective year, rather than rainfall. The microorganisms’ activity in soil produces more CO₂ during summer and autumn. Therefore, the water nature of springs in silicate regions chiefly reflects the seasonal changes of CO₂ produced by the microorganisms in soil.     

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.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.The online version of the original article can be found at     

Environmental isotopic and hydrochemical study of water in the karst aquifer and submarine springs of the Syrian coast

The groundwater of major karst systems and submarine springs in the coastal limestone aquifer of Syria has been investigated using chemical and isotopic techniques. The δ¹⁸O values of groundwater range from ?6.8 to ?5.05‰, while those for submarine springs vary from ?6.34 to +1.08‰ (eastern Mediterranean seawater samples have a mean of +1.7‰). Groundwater originates from the direct infiltration of atmospheric water. Stable isotopes show that the elevation of the recharge zones feeding the Banyas area (400–600 m a.s.l.) is higher than that feeding the Amrit area (100–300 m a.s.l.). The ¹⁸O_extracted (¹⁸O content of the seawater contribution) for the major submarine springs suggests a mean recharge area elevation of 600–700 m a.s.l., and lower than 400 m a.s.l. for the spring close to Amrit. Based on the measured velocity and the percentage of fresh water at the submarine springs outlet, the estimated discharge rate is 350 million m³/year. The tritium concentrations in groundwater (1.6–5.9 TU) are low and very close to the current rainfall values (2.9–5.6 TU). Adopting a model with exponential time distribution, the mean turnover time of groundwater in the Al-sen spring was evaluated to be 60 years. A value of about 3.7 billion m³ was obtained for the maximum groundwater reservoir size.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.An erratum to this article can be found at     

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.     

Impact of lake‐level changes on the formation of thermogene travertine in continental rifts: Evidence from Lake Bogoria,Kenya Rift Valley

Travertine is present at 20% of the ca 60 hot springs that discharge on Loburu delta plain on the western margin of saline, alkaline Lake Bogoria in the Kenya Rift. Much of the travertine, which forms mounds, low terraces and pool‐rim dams, is sub‐fossil (relict) and undergoing erosion, but calcite‐encrusted artefacts show that carbonate is actively precipitating at several springs. Most of the springs discharge alkaline (pH: 8·3 to 8·9), Na‐HCO₃ waters containing little Ca (<2 mg l^?1) at temperatures of 94 to 97·5°C. These travertines are unusual because most probably precipitated at temperatures of >80°C. The travertines are composed mainly of dendritic and platy calcite, with minor Mg‐silicates, aragonite, fluorite and opaline silica. Calcite precipitation is attributed mainly to rapid CO₂ degassing, which led to high‐disequilibrium crystal morphologies. Stratigraphic evidence shows that the travertine formed during several stages separated by intervals of non‐deposition. Radiometric ages imply that the main phase of travertine formation occurred during the late Pleistocene (ca 32 to 35 ka). Periods of precipitation were influenced strongly by fluctuations in lake level, mostly under climate control, and by related changes in the depth of boiling. During relatively arid phases, meteoric recharge of ground water declines, the lake is low and becomes hypersaline, and the reduced hydrostatic pressure lowers the level of boiling in the plumbing system of the hot springs. Any carbonate precipitation then occurs below the land surface. During humid phases, the dilute meteoric recharge increases, enhancing geothermal circulation, but the rising lake waters, which become relatively dilute, flood most spring vents. Much of the aqueous Ca²⁺ then precipitates as lacustrine stromatolites on shallow firm substrates, including submerged older travertines. Optimal conditions for subaerial travertine precipitation at Loburu occur when the lake is at intermediate levels, and may be favoured during transitions from humid to drier conditions.