Chemical and stable isotopic models for boundary creek warm springs, southwestern Yellowstone National Park, Wyoming

Thermal springs of the Boundary Creek hydrothermal system in the southwestern part of Yellowstone Park outside the caldera boundary vary in chemical and isotopic composition, and temperature. The diversity may be accounted for by a combination of processes including boiling of a deep thermal water, mixing of the deep thermal water with cool meteoric water and/or with condensed steam or steam-heated meteoric water, and chemical reactions with surrounding rocks. Dissolved-silica, Na⁺, K⁺ and Ca²⁺ contents of the thermal springs could result from a thermal fluid with a temperature of 200 ± 20°C. Chloride-enthalpy and silica-enthalpy mixing models suggest mixing of 230°C, 220 mg/l Cl⁻ thermal water with cool, low-Cl⁻ components. A 350 to 390°C component with Cl⁻ ≥ 300 mg/l is possibly present in thermal springs inside the caldera but is not required to fit observed spring chemical and isotopic compositions. Irreversible mass transfer models in which a low-temperature water reacts with volcanic glass as it percolates downward and warms, can account for observed pH and dissolved-silica, K⁺, Na⁺, Ca²⁺ and Mg²⁺ concentrations, but produces insufficient Cl⁻ or F⁻ for measured concentrations in the warm springs. The ratio of a_Na/a_H, and Cl⁻ are best accounted for in mixing models. The water-rock interaction model fits compositions of acid-sulfate waters observed at Summit Lake and of low-Cl⁻ waters involved in mixing.The cold waters collected from southwestern Yellowstone Park have δD values ranging from −118 to −145 per mil and δ¹⁸O values of −15.9 to −19.4 per mil. Two samples from nearby Island Park have δD values of −112 and −114 per mil and δ¹⁸O values of −15.1 and −15.3 per mil. All samples of thermal water plot significantly to the right of the meteoric water line. The low Cl⁻ and variable δD values of the thermal waters indicate isotopic compositions are derived by extensive dilution with cold meteoric water and by steam separation on ascent to the surface. Many of the hot springs with higher δD values may contain in addition a significant amount of high-D, low-Cl⁻, acid-sulfate or steam-heated meteoric water. Mixing models, Cl⁻ content and isotopic compositions of thermal springs suggest that 30% or less of a deep thermal component is present. For example, the highest-temperature springs from Three Rivers, Silver Scarf and Upper Boundary Creek thermal areas contain up to 70% cool meteoric water and 30% hot water components, springs at Summit Lake and Middle Boundary Creek spring 57 are acid-sulfate or steam-heated meteoric water; springs 27 and 48 from Middle Boundary Creek and 49 from Mountain Ash contain in excess of 50% acid-sulfate water; and Three Rivers spring 46 and Phillips could result from mixing hot water with 55% cool meteoric water followed by mixing of acid-sulfate water. Extensive dilution by cool meteoric water increases the uncertainties in quantity and nature of the deep meteoric, thermal component.     

Hydrogen and oxygen isotope ratios in the waters of the Ngawha hydrothermal area,North Auckland

The ratios of D/H and O¹⁸/O¹⁶ in natural waters from streams, boreholes, soda springs, hot pools, ponds and larger bodies of water in the Ngawha hydrothermal area were determined. The results are considered in relation to the isotopic changes known to occur in water subjected to evaporation. Where applicable chemical and other work was also considered. It is assumed that stream water isotope composition is the mean value for the isotopic composition of meteoric waters. Measurements on waters taken from boreholes drilled to 65 feet and 350 feet and from the other water sources mentioned, indicate that they were of meteoric origin as judged by stream isotope composition. The waters from the soda springs appeared to be isotopically the same as the stream water, a finding consistent with the absence of evaporative surface. These borehole waters were similar but slightly different in O¹⁸ due probably to exchange between rock and water. Heavy isotope enrichment of the ponds and larger bodies of water appeared to be due to non-equilibrium evaporation at ambient temperature. The hot pools in the Ngawha springs area proper were enriched in the heavier isotopes probably due to non-equilibrium evaporation at the usual hot pool temperature of about 40°C and also to exchange of O¹⁸ between water and rock. The water from a further borehole drilled to approximately 2,000 feet appeared also to be of meteoric origin but was changed in O¹⁸ content to an extent consistent with the assumption that oxygen isotope exchange with rock had taken place at approximately 230°C. The results are used to illustrate possibilities for the use of oxygen and hydrogen isotope measurements in hydrothermal investigations.     

Sr isotope diversity of hot spring and volcanic lake waters from Zao volcano,Japan

The ratio of ⁸⁷Sr/⁸⁶Sr was measured from different water samples of thermal/mineral (hot spring as well as crater lake) and meteoric origins, in order to specify the location and to verify the detailed model of a volcano-hydrothermal system beneath Zao volcano. The ratio showed a trimodal distribution for the case of thermal/mineral water: 0.7052–0.7053 (Type A, Zao hot spring), 0.7039–0.7043 (Type B, Okama crater lake and Shin-funkiko hot spring), and 0.7070–0.7073 (Type C, Gaga, Aone, and Togatta hot springs), respectively. However, in comparison, the ratio was found to be higher for meteoric waters (0.7077–0.7079). The water from the central volcanic edifice (Type B) was found to be similar to that of nearby volcanic rocks in their Sr isotopic ratio. This indicates that the Sr in water was derived from shallow volcanic rocks. The ⁸⁷Sr/⁸⁶Sr ratio for water from the Zao hot spring (Type A) was intermediate between those of the pre-Tertiary granitic and the Quaternary volcanic rocks, thus suggesting that the water had reacted with both volcanic and granitic rocks. The location of the vapor–liquid separation was determined as the boundary of the pre-Tertiary granitic and the Quaternary volcanic rocks by comparing the results of this strontium isotopic study with those of Kiyosu and Kurahashi [Kiyosu, Y., Kurahashi, M., 1984. Isotopic geochemistry of acid thermal waters and volcanic gases from Zao volcano in Japan. J. Volcanol. Geotherm. Res. 21, 313–331.].     

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

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

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

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

Fluid geochemistry of natural manifestations from the Southern Poroto–Rungwe hydrothermal system (Tanzania): Preliminary conceptual model

The South Poroto–Rungwe geothermal field, in the northern part of the Malawi rift, Tanzania divides in two main areas. The relatively high altitude northern area around the main Ngozi, Rungwe, Tukuyu and Kyejo volcanoes, is characterised by cold and gas-rich springs. In contrast, hot springs occur in the southern and low-altitude area between the Kyela and Livingstone faults. The isotopic signature of the almost stagnant, cold springs of the Northern district is clearly influenced by H₂O–CO_2(g) exchange as evidenced from negative oxygen-shifts in the order of few deltas permil. In contrast, the isotopic signature of waters discharged from the hot springs of the Southern district is markedly less affected by the H₂O–CO_2(g) interaction. This evidence is interpreted as an effect of the large, permanent outflow of these springs, which supports the hypothesis of a regional-scale recharge of the major thermal springs. Measurements of carbon isotope variations of the dissolved inorganic carbon of waters and CO_2(g) from the Northern and Southern springs support a model of CO_2(g)-driven reactivity all over the investigated area. Our combined chemical and isotopic results show that the composition of hot springs is consistent with a mixing between (i) cold surface fresh (SFW) and (ii) Deep Hot Mineralised (DHMW) Water, indicating that the deep-originated fluids also supply most of the aqueous species dissolved in the surface waters used as local potable water. Based on geothermometric approaches, the temperature of the deep hydrothermal system has been estimated to be higher than 110 °C up to 185 °C, in agreement with the geological and thermal setting of the Malawi rift basin. Geochemical data point to (i) a major upflow zone of geothermal fluids mixed with shallow meteoric waters in the Southern part of the province, and (ii) gas absorption phenomena in the small, perched aquifers of the Northern volcanic highlands.     

Contribution to the detection of Lake Masoko (Tanzania) groundwater outflow: isotopic evidence (18O,D) / Contribution à la détection des pertes souterraines du Lac Masoko (Tanzanie): évidences isotopiques (18O,D)

Abstract

The isotopic compositions (¹⁸O and D) of groundwater, springs, rivers and lake waters are used to account for the hydrological processes in the area of the closed maar Lake Masoko in Tanzania. Springs and groundwater from the northern, western and southern parts of the lake basin display relatively stable compositions, close to those of the mean precipitation, evidencing their fast infiltration rate. Springs located in the eastern part of the basin have enriched compositions, which are on the mixing line between the ?"non evaporated? water and the evaporated lake water. This underlines the hydraulic continuity between the lake and the eastern springs and supports a previous proposition of grounwater outflow from Lake Masoko. The mixing parts of lake water calculated at each spring are constant through time, evidencing the inertia of the system. Furthermore, the mixing part of the lake water decreases linearly with the distance from the lake, suggesting an homogeneous and continuous aquifer. These observations point to a west to east groundwater flow, in agreement with the altitude of different potentials.     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

Local vs. Regional Groundwater Flow Delineation from Stable Isotopes at Western North America Springs

The recharge location for many springs is unknown because they can be sourced from proximal, shallow, atmospheric sources or long‐traveled, deep, regional aquifers. The stable isotope (¹⁸O and ²H) geochemistry of springs water can provide cost‐effective indications of relative flow path distance without the expense of drilling boreholes, conducting geophysical studies, or building groundwater flow models. Locally sourced springs generally have an isotopic signature similar to local precipitation for that region and elevation. Springs with a very different isotopic composition than local meteoric inputs likely have non‐local recharge, representing a regional source. We tested this local vs. regional flow derived hypothesis with data from a new, large springs isotopic database from studies across Western North America in Arizona, Nevada, and Alberta. The combination of location‐specific precipitation data with stable isotopic groundwater data provides an effective method for flow path determination at springs. We found springs in Arizona issue from a mix of regional and local recharge sources. These springs have a weak elevation trend across 1588 m of elevation where higher elevation springs are only slightly more depleted than low elevation springs with a δ¹⁸O variation of 5.9‰. Springs sampled in Nevada showed a strong elevation‐isotope relationship with high‐elevation sites discharging depleted waters and lower elevation springs issuing enriched waters; only a 2.6‰ difference exists in ¹⁸O values over an elevation range of more than 1500 m. Alberta's springs are mostly sourced from local flow systems and show a moderate elevation trend of 1200 m, but the largest range in δ¹⁸O, 7.1‰.     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.     

Geochemical and isotopic evidence for seawater contamination of the hydrothermal system of Taal Volcano, Luzon, the Philippines

 The hydrologic structure of Taal Volcano has favored development of an extensive hydrothermal system whose prominent feature is the acidic Main Crater Lake (pH<3) lying in the center of an active vent complex, which is surrounded by a slightly alkaline caldera lake (Lake Taal). This peculiar situation makes Taal prone to frequent, and sometimes catastrophic, hydrovolcanic eruptions. Fumaroles, hot springs, and lake waters were sampled in 1991, 1992, and 1995 in order to develop a geochemical model for the hydrothermal system. The low-temperature fumarole compositions indicate strong interaction of magmatic vapors with the hydrothermal system under relatively oxidizing conditions. The thermal waters consist of highly, moderately, and weakly mineralized solutions, but none of them corresponds to either water–rock equilibrium or rock dissolution. The concentrated discharges have high Na contents (>3500 mg/kg) and low SO₄/Cl ratios (<0.3). The Br/Cl ratio of most samples suggests incorporation of seawater into the hydrothermal system. Water and dissolved sulfate isotopic compositions reveal that the Main Crater Lake and spring discharges are derived from a deep parent fluid (T≈300  °C), which is a mixture of seawater, volcanic water, and Lake Taal water. The volcanic end member is probably produced in the magmatic-hydrothermal environment during absorption of high-temperature gases into groundwater. Boiling and mixing of the parent water give rise to the range of chemical and isotopic characteristics observed in the thermal discharges. Incursion of seawater from the coastal region to the central part of the volcano is supported by the low water levels of the lakes and by the fact that Lake Taal was directly connected to the China sea until the sixteenth century. The depth to the seawater-meteoric water interface is calculated to be 80 and 160 m for the Main Crater Lake and Lake Taal, respectively. Additional data are required to infer the hydrologic structure of Taal. Geochemical surveillance of the Main Crater Lake using the SO₄/Cl, Na/K, or Mg/Cl ratio cannot be applied straightforwardly due to the presence of seawater in the hydrothermal system. Received: 12 February 1997 / Accepted: 26 January 1998     

87Rb-87Sr studies of waters in a geothermal area: The Cantal,France

We have determined K, Rb and Sr concentrations and⁸⁷Sr/⁸⁶Sr ratios in fresh surface waters, a rain water sample and five geothermal waters from the Cantal volcanic area in the Massif Central, France. A comparison with appropriate rock types of the region showed no apparent chemical and isotopic fractionation occurring in the fresh water-surface rock system. The thermo-mineral water results suggest that all springs discharge dissolved Sr from the following contributors: Hercynian granito-metamorphic basement, lacustrian sediments underlying the volcano, Miocene-Pliocene volcanic rocks of basaltic to rhyolitic composition.     

Time scale of hydrothermal water-rock reactions in Yellowstone National Park based on radium isotopes and radon

We have measured ²²⁴Ra (3.4 d), ²²⁸Ra (5.7 yr), and ²²⁶Ra (1620 yr) and chloride in hot spring waters from the Norris-Mammoth Corridor, Yellowstone National Park. Two characteristic cold-water components mix with the primary hydrothermal water: one for the travertine-depositing waters related to the Mammoth Hot Springs and the other for the sinter-depositing Norris Geyser Basin springs. The Mammoth Hot Springs water is a mixture of the primary hydrothermal fluid with meteoric waters flowing through the Madison Limestone, as shown by the systematic decrease of the (²²⁸Ra/²²⁶Ra) activity ratio proceeding northward. The Norris Geyser Basin springs are mixtures of primary hydrothermal water with different amounts of cold meteoric water with no modification of the primary hydrothermal (²²⁸Ra/²²⁶Ra) activity ratio. Using a solution and recoil model for radium isotope supply to the primary hydrothermal water, a mean water-rock reaction time prior to expansion at 350°C and supply to the surface is 540 years assuming that 250 g of water are involved in the release of the radium from one gram of rock. The maximum reaction time allowed by our model is 1150 years.     

The hydrothermal system of Nevado del Ruiz volcano,Colombia

Hot springs and steam vents on the slopes of Nevado del Ruiz volcano provide evidence regarding the nature of hydrothermal activity within the summit and flanks of the volcano. At elevations below 3000 m, alkali-chloride water is discharged from two groups of boiling springs and several isolated warm springs on the western slope of Nevado del Ruiz. Chemical and isotopic geothermometers suggest that the boiling springs are fed by an aquifer having a subsurface equilibration temperature of at least 175°C, and the sampled warm spring is fed by an aquifer having a subsurface equilibration temperature near 150°C. Similarities in conservative solute ratios (e.g., B/Cl) indicate that the alkali-chloride waters may be related to a single reservoir at depth. Isotopic ratios of hydrogen and oxygen indicate that recharge for the alkali-chloride aquifers comes mostly from higher elevations on the volcano. Steam vents and steam-heated bicarbonate-sulfate springs at higher elevations, along a linear structural trend with the alkali-chloride springs, may be derived partly from the alkali-chloride water at depth by boiling. Steam from the vents (84°C) yields a gas geothermometer temperature of 209°C. Acid-sulfate-chloride and acid-sulfate waters are discharged widely from warm springs above 3000 m on the northern and eastern slopes of Nevado del Ruiz. Similarities in B/Cl and SO₄/Cl ratios suggest that the acid waters are mixtures of water from an acid-sulfate-chloride reservoir with various proportions of shallow, dilute groundwater. The major source of sulfate, halogens, and acidity for the acid waters may be high-temperature magmatic gases. Available data on hot spring temperatures and compositions indicate that they have remained fairly stable since 1968. However, the eruption of November 13, 1985 apparently caused an increase in sulfate concentration in some of the acid springs that peaked about a year after the eruption. Long-term monitoring of hot spring compositions over many years will be required to better define the effects of volcanic activity on the Nevado del Ruiz hydrothermal system.     

Natural tracers for identifying the origin of the thermal fluids emerging along the Aegean Volcanic arc (Greece): Evidence of Arc-Type Magmatic Water (ATMW) participation

The Aegean volcanic arc is the result of a lithosphere subduction process during the Quaternary time. Starting from the Soussaki area, from west to east, the arc proceeds through the islands of Egina, Methana, Milos, Santorini, the Columbus Bank, Kos and Nisyros. Volcano-tectonic activities are still pronounced at Santorini and Nisyros in form of seismic activity, craters of hydrothermal explosions, hot fumaroles and thermal springs. A significant number of cold water springs emerge in the vicinity of hot waters on these islands.Chemical and isotopic analyses were applied on water and fumaroles samples collected in different areas of the volcanic arc in order to attempt the assessment of these fluids. Stable isotopes of water and carbon have been used to evaluate the origin of cold and thermal water and CO₂.Chemical solute concentrations and isotopic contents of waters show that the fluids emerging in Egina, Soussaki, Methana and Kos areas represent geothermal systems in their waning stage, while the fluids from Milos, Santorini and Nisyros proceed from active geothermal systems.The δ²H–δ¹⁸O–Cl^? relationships suggest that the parent hydrothermal liquids of Nisyros and Milos are produced through mixing of seawater and Arc-Type Magmatic Water (ATMW), with negligible to nil contribution of local ground waters and with very high participation of the magmatic component, which is close to 70% in both sites. A very high magmatic contribution to the deep geothermal system could occur at Santorini as well, perhaps with a percentage similar to Nisyros and Milos, but it cannot be calculated because of steam condensation heavily affecting the fumarolic fluids of Nea Kameni before the surface discharge.The parent hydrothermal liquid at Methana originates through mixing of local groundwaters, seawater and ATMW, with a magmatic participation close to 19%. All in all, the contribution of ATMW is higher in the central–eastern part of the Aegean volcanic arc than in the western sector. This difference, which is spotted in the variable isotopic composition of the sampled fluids from west to east along the arc, is probably due to several causes, including the tectonic regime, the depth of the deep reservoir below sea level, the age of volcanic activity and in general the geomorphologic state of each island.     

Geochemistry of Quaternary travertines in the region north of Rome (Italy): structural, hydrologic and paleoclimatic implications

In the Tyrrhenian region of central Italy, late Quaternary fossil travertines are widespread along two major regional structures: the Tiber Valley and the Ancona-Anzio line. The origin and transport of spring waters from which travertines precipitate are elucidated by chemical and isotopic studies of the travertines and associated thermal springs and gas vents. There are consistent differences in the geochemical and isotopic signatures of thermal spring waters, gas vents and present and fossil travertines between east and west of the Tiber Valley. West of the Tiber Valley, δ¹³C of CO₂ discharged from gas vents and δ¹³C of fossil travertines are higher than those to the east. To the west the travertines have higher strontium contents, and gases emitted from vents have higher ³He/⁴He ratios and lower N₂ contents, than to the east. Fossil travertines to the west have characteristics typical of thermogene (thermal spring) origin, whereas those to the east have meteogene (low-temperature) characteristics (including abundant plant casts and organic impurities). The regional geochemical differences in travertines and fluid compositions across the Tiber Valley are interpreted with a model of regional fluid flow. The regional Mesozoic limestone aquifer is recharged in the main axis of the Apennine chain, and the groundwater flows westward and is discharged at springs. The travertine-precipitating waters east of the Tiber Valley have shallower flow paths than those to the west. Because of the comparatively short fluid flow paths and low (normal) heat flow, the groundwaters to the east of the Tiber Valley are cold and have CO₂ isotopic signatures, indicating a significant biogenic contribution acquired from soils in the recharge area and limited deeply derived CO₂. In contrast, spring waters west of the Tiber Valley have been conductively heated during transit in these high heat-flow areas and have incorporated a comparatively large quantity of CO₂ derived from decarbonation of limestone. The elevated strontium content of the thermal spring water west of the Tiber Valley is attributed to deep circulation and dissolution of a Triassic evaporite unit that is stratigraphically beneath the Mesozoic limestone. U-series age dates of fossil travertines indicate three main periods of travertine formation (ka): 220-240, 120-140 and 60-70. Based on the regional flow model correlating travertine deposition at thermal springs and precipitation in the recharge area, we suggest that pluvial activity was enhanced during these periods. Our study suggests that travertines preserve a valuable record of paleofluid composition and paleoprecipitation and are thus useful for reconstructing paleohydrology and paleoclimate.     

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

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

Geochemical evidence of hydrothermal recharge in Lake Baringo,central Kenya Rift Valley

Lake Baringo, a freshwater lake in the central Kenya Rift Valley, is fed by perennial and ephemeral rivers, direct rainfall, and hot springs on Ol Kokwe Island near the centre of the lake. The lake has no surface outlet, but despite high evaporation rates it maintains dilute waters by subsurface seepage through permeable sediments and faulted lavas. New geochemical analyses (major ions, trace elements) of the river, lake, and hot spring waters and the suspended sediments have been made to determine the main controls of lake water quality. The results show that evaporative concentration and the binary mixing between two end members (rivers and thermal waters) can explain the hydrochemistry of the lake waters. Two zones are recognized from water composition. The southern part of the lake near sites of perennial river inflow is weakly influenced by evaporation, has low total dissolved species (TDS), and has a seasonally variable load of mainly detrital suspended sediments. In contrast, waters of the northern part of the lake show evidence for strong evaporation (TDS of up to eight times inflow). Authigenic clay minerals and calcite may be precipitating from those more concentrated fluids. The subaerial hot‐spring waters have a distinctive chemistry and are enriched in some elements that are also present in the lake water. Comparison of the chemical composition of the inflowing surface waters and lake water shows (1) an enrichment of some species (HCO₃^?, Cl, SO₄^2?, F, Na, B, V, Cr, As, Mo, Ba and U) in the lake, (2) a depletion in SiO₂ in the lake, and (3) a possible hydrothermal origin for most F. The rare earth element distribution and the F/Cl and Na/Cl ratios give valuable information on the rate of mixing of the river and hydrothermal fluids in the lake water. Calculations imply that thermal fluids may be seeping upward locally into the lake through grid‐faulted lavas, particularly south of Ol Kokwe Island. Copyright © 2006 John Wiley & Sons, Ltd.     

Environmental isotope study on hydrodynamics of Lake Naini,Uttar Pradesh,India

Environmental isotopes (δ¹⁸O, δD and ³H) were used to understand the hydrodynamics of Lake Naini in the State of Uttar Pradesh, India. The data was correlated with the in situ physico‐chemical parameters, namely temperature, electrical conductivity and dissolved oxygen. The analysis of the data shows that Lake Naini is a warm monomictic lake [i.e. in a year, the lake is stratified during the summer months (March/April to October/November) and well mixed during the remaining months]. The presence of a centrally submerged ridge inhibits the mixing of deeper waters of the lake's two sub‐basins, and they exhibit differential behaviour. The rates of change of isotopic composition of hypolimnion and epilimnion waters of the lake indicate that the water retention time of the lake is very short, and the two have independent inflow components. A few groundwater inflow points to the lake are inferred along the existing fractures, fault planes and dykes. In addition to poor vertical mixing of the lake due to the temperature‐induced seasonal stratification, the lake also shows poor horizontal mixing at certain locations of the lake. The lake–groundwater system appears to be a flow‐through type. Also, a tritium and water‐balance model was developed to estimate the water retention time of well‐mixed and hydrologically steady state lakes. The model assumes a piston flow of groundwater contributing to the lake. The developed model was verified for (a) Finger Lakes, New York; (b) Lake Neusiedlersee, Austria; and (c) Blue Lake, Australia based on literature data. The predicted water retention times of the lakes were close to those reported or calculated from the hydrological parameters given in the references. On application of this model to Lake Naini, a water retention time of ～2 years and age of groundwater contributing to the lake ～14 years is obtained. Copyright © 2001 John Wiley & Sons, Ltd.     

Spatial and temporal variability of stable isotopes (δ18O and δ2H) in surface waters of arid,mountainous Central Asia

Characterization of spatial and temporal variability of stable isotopes (δ¹⁸O and δ²H) of surface waters is essential to interpret hydrological processes and establish modern isotope–elevation gradients across mountainous terrains. Here, we present stable isotope data for river waters across Kyrgyzstan. River water isotopes exhibit substantial spatial heterogeneity among different watersheds in Kyrgyzstan. Higher river water isotope values were found mainly in the Issyk‐Kul Lake watershed, whereas waters in the Son‐Kul Lake watershed display lower values. Results show a close δ¹⁸O–δ²H relation between river water and the local meteoric water line, implying that river water experiences little evaporative enrichment. River water from the high‐elevation regions (e.g., Naryn and Son‐Kul Lake watershed) had the most negative isotope values, implying that river water is dominated by snowmelt. Higher deuterium excess (average d = 13.9‰) in river water probably represents the isotopic signature of combined contributions from direct precipitation and glacier melt in stream discharge across Kyrgyzstan. A significant relationship between river water δ¹⁸O and elevation was observed with a vertical lapse rate of 0.13‰/100 m. These findings provide crucial information about hydrological processes across Kyrgyzstan and contribute to a better understanding of the paleoclimate/elevation reconstruction of this region.