Deep groundwater flow and geochemical processes in limestone aquifers: evidence from thermal waters in Derbyshire, England, UK

Thermal waters potentially provide information on geochemical processes acting deep within aquifers. New isotopic data on groundwater sulphate, inorganic carbon and strontium in thermal and non-thermal waters of a major limestone aquifer system in Derbyshire, England, UK, are used to constrain sulphate sources and groundwater evolution. Shallow groundwaters gain sulphate from oxidation of sulphide minerals and have relatively ¹³C-depleted dissolved inorganic carbon (DIC). Thermal waters have relatively high Sr/Ca and more ¹³C-enriched DIC as a result of increased water–rock interaction. In other respects, the thermal waters define two distinct groups. Thermal waters rising at Buxton have higher Mg, Mn and ⁸⁷Sr/⁸⁶Sr and lower Ca and SO₄, indicating flow from deep sandstone aquifers via a high permeability pathway in the limestone. By contrast, Matlock-type waters (97% of the thermal flux) have elevated sulphate concentrations derived from interaction with buried evaporites, with no chemical evidence for flow below the limestone. About 5% of the limestone area's groundwater flows to the Matlock group springs via deep regional flow and the remainder flows via local shallow paths to many non-thermal springs. Gypsum dissolution has produced significant tertiary porosity and tertiary permeability in the carbonate aquifer and this is an essential precursor to the development of karstic drainage.

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Resumen Las aguas termales potencialmente proporcionan información sobre procesos geoquímicos que actúan a profundidad en acuíferos. Nuevos datos isotópicos de sulfatos, carbón inorgánico y estroncio en aguas termales y no-termales de un acuífero importante de caliza en Derbyshire, Inglaterra se utilizan para delinear las fuentes de sulfato y la evolución de aguas subterráneas.Las aguas subterráneas no muy profundas adquieren sulfato a través de la oxidación de minerales de sulfuro y poseen carbón inorgánico disuelto (DIC) relativamente deplatado de ¹³C. Las aguas termales muestran un ratio Sr/Ca relativamente alto y poseen (DIC) más enriquecido en¹³C, como resultado de la mayor interacción de roca-agua. En otros aspectos, los aguas termales definen dos grupos distintivos. Las aguas termales que ascienden en Buxton tienen mas Mg, Mn y ⁸⁷Sr/⁸⁶Sr y menos Ca and SO₄, indicando flujo de acuíferos de areniscas profundas por un sendero de alta permeabilidad en la caliza.En contraste el tipo de agua - Matlock (97% del flujo termal) posee altas concentraciones de sulfato, derivado por interacción con evaporitas enterradas, sin evidencia química de flujo debajo de la caliza. Aproximadamente 5% del agua del área de la caliza se fluye al grupo de manantiales de Matlock a través de un flujo regional profundo y el resto fluye por senderos locales poco profundos a muchos de los manantiales no-termales. La disolución de yeso ha producido porosidad terciaria importante así como permeabilidad en el acuífero de carbonato y este es un precursor esencial del desarrollo de drenaje kárstico.

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Résumé Les eaux thermales peuvent apporter des informations sur les processus géochimiques dans les aquifères profonds. De nouvelles données isotopiques sur les sulfates présents dans les eaux souterraines, le carbone inorganique et le strontium dans les eaux thermales et non thermales d'un système aquifère calcaire majeur dans le Derbyshire, Angleterre, Royaume Uni, sont utilisées pour comprendre les sources de sulfates et l'évolution des eaux souterraines. Les eaux souterraines phréatique s'enrichissent en sulfate via l'oxydation des minéraux sulfatés et ont un Carbone Inorganique Dissous (DIC) relativement appauvri en¹³C. Les eaux thermales ont un rapport Sr/Ca relativement plus élevé et un DIC plus enrichi en¹³C, du fait de l'interaction accrue des eaux avec les roches. En d'autres mots, les eaux thermales définissent deux groupes distincts. Les eaux thermales remontant à Buxton ont un Mg, un Mn et un rapport ⁸⁷Sr/⁸⁶Sr plus hauts, mais un Ca et SO₄ plus faible, indiquant un écoulement à travers les zones perméables des aquifers gréseux. Par contraste, les eaux du type de Matlock (97% du flux thermique), possèdent des concentrations élevées en sulfates, provenant de l'interaction des eaux avec les évaporites enfouies, tandis qu'il n'existe aucune évidence chimique d'un écoulement sous les calcaires. Sur environ 5% de la surface des calcaires, les eaux souterraines alimentent des sources non-thermales. La dissolution du Gypse a produit une porosité tertiaire significative et une perméabilité dans les aquifères calcaires, et ceci est un précurseur essentiel au développement du drainage karstique.

     

Hydrochemical and isotopic behaviour of a Saharan phreatic aquifer suffering severe natural and anthropic constraints (case of Oued-Souf region, Algeria)

An approach combining the use of water dissolved chemical species and isotopic fingerprints has been used to understand the behavior of a phreatic aquifer and to determine the origin of its different water components. This aquifer is located in the large sedimentary basin of the Great Oriental Erg (Algeria) and overlies two deeper aquifers: the Complexe Terminal (CT) and the Continental Intercalaire (CI). Besides the deterioration of its groundwater quality, its water table has risen during the last 20 years. A water budget surplus between 950 and 2500 l s^?1 was estimated. Down-gradient groundwater evolution (south-north) has shown that the mineralisation increases from 1.23 to 5.20 g l^?1 due to evaporite minerals dissolution. Chemical and isotopic data demonstrated that in addition to rainfall there is a contribution from the CT and CI aquifers. The latter are tritium-free and less mineralized than the phreatic aquifer. Their radiocarbon contents are very low (<10 pmC, percent modern Carbon) (Pleistocene recharge) whereas quite the contrary is observed for the superficial aquifer which exhibits fairly high and variable C-14 activities (50–100 pmC), evidence of recent recharge. On the basis of tritium contents, two groundwater groups were identified for the phreatic aquifer.     

Hydrogeochemical processes,mixing and isotope tracing in hard rock aquifers and surface waters from the Subarnarekha River Basin, (east Singhbhum District,Jharkhand State,India)

Geochemical observations, including major ion and trace element analysis, and isotopic tracing have been carried out in the Subarnarekha River system (northeastern India) during a surface-water- and groundwater-monitoring program aimed at evaluating impacts of mining. The aquifer is of fracture type. Groundwater flow conditions and pollutant transfer were observed through a network of 69 wells. δ¹⁸O and δ²H results suggest that transfer from rainfall towards groundwater storage through soils and the unsaturated zone is fast, without any major transformation like evaporation. The scatter of ⁸⁷Sr/⁸⁶Sr signatures in surface water and groundwater are explained by three end-members. One is compatible with rainwater inputs. The most mineralised end-member represents anthropogenic inputs (agricultural practices and ore processing). The third end-member, characterised by a high ⁸⁷Sr/⁸⁶Sr signature, is believed to be controlled by natural geochemical processes, although affected by human activities (e.g. drainage of mine waste). Potential flow paths, investigated north of the area, reveal that all groundwater types seem to evolve more in pockets than along a flow path. The limited extent of transfer and the predominance of natural phenomena help to explain the moderate level of groundwater contamination and the characteristics of surface water contamination by mining and the metallurgy industry.     

Use of hydrogeochemistry and environmental isotopes for evaluation of groundwater in Qingshuihe Basin,northwestern China

Hydrogeochemistry and environmental isotope data were utilized to understand origin, geochemical evolution, hydraulic interconnection, and renewability of groundwater in Qingshuihe Basin, northwestern China. There are four types of groundwater: (1) shallow groundwater in the mountain front pluvial fans, originating from recent recharge by precipitation, (2) deep paleo-groundwater of the lower alluvial plains, which was formed long ago, (3) shallow groundwater in the lower alluvial plains, which has undergone evaporation during the recharge process, and (4) mixed groundwater (shallow and deep groundwater in the plain). The main water types are Na–HCO₃, which dominates type (1), and Na–SO₄, which dominates types (2) and (3). Geochemical evolution in the upper pluvial fans is mainly the result of CO₂ gas dissolution, silicates weathering and cation exchange; in the lower alluvial plains, it is related to mineral dissolution. The evaporative enrichment only produces significant salinity increases in the shallow groundwater of the lower alluvial plains. Shallow groundwater age in the upper plain is 10 years or so, showing a strong renewability. Deep groundwater ages in the lower plain are more than 200 years, showing poor renewability. In the exploitation areas, the renewability of groundwater evidently increases and the circulation period is 70–100 years.     

The hydrochemical characteristics and evolution of groundwater and surface water in the Heihe River Basin, northwest China

A combination of isotopic and chemical indicators has been used to characterize rainfall, surface water and groundwater in the Heihe River Basin, China. Surface- vs. groundwater chemistry data enabled geographical zones and chemical types to be differentiated. The dissolution of halite, Glauber’s salt, gypsum, dolomite and calcite determine Na⁺, Cl^?, Mg²⁺, Ca²⁺, $ {\text{SO}}^{{2 - }}_{4} A combination of isotopic and chemical indicators has been used to characterize rainfall, surface water and groundwater in the Heihe River Basin, China. Surface- vs. groundwater chemistry data enabled geographical zones and chemical types to be differentiated. The dissolution of halite, Glauber’s salt, gypsum, dolomite and calcite determine Na⁺, Cl⁻, Mg²⁺, Ca²⁺, and chemistry, but other processes such as evaporation, ion exchange, and deposition also influence the water composition. The majority of deep confined groundwaters are tritium-free and less mineralized than in the shallow aquifer. Radiocarbon values in the deeper groundwaters range from 18.8 to 38.9 pmc, and 80 pmc probably represents the upper limit of initial ¹⁴C activity; this yields ages of approximately 5,960–11,971 years BP, which is about 3,000 years older than those calculated by models in previous work. The shallow aquifer exhibits fairly high and variable tritium activities (4–75 TU), evidence of recent recharge and low residence time (<60 years), which is in line with estimates from previous work. Isotopic signatures indicate formation of deeper groundwaters in a colder and wetter climate during the late Pleistocene and Holocene. The results suggested that significant changes are urgently needed in water-use strategy to achieve sustainable development.

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Résumé Une combinaison de plusieurs indicateurs isotopiques et chimiques a été utilisée dans le but de caractériser les précipitations, les eaux de surface et les eaux souterraines dans le Bassin de la Rivière Heihe, en Chine. La confrontation des chimies des eaux souterraines et de surface a permis de différentier plusieurs secteurs géographiques et faciès chimiques. Les compositions chimiques en Na⁺, Cl⁻, Mg²⁺, Ca²⁺, et sont déterminées par la dissolution de la halite, du sel de Glauber, du gypse, de la dolomite et de la calcite, mais d’autres processus peuvent également avoir une influence, comme l’évaporation, les échanges de bases et la sédimentation. La majorité des eaux souterraines captives profondes ne contiennent pas de tritium, et sont moins minéralisées que dans l’aquifère superficiel. Les valeurs de carbone 14 dans l’aquifère le plus profond sont comprises entre 18.8 et 38.9 pcm, pour une valeur maximum probable d’activité initiale de 80 pcm; les ages estimés correspondants sont compris entre 5,960 et 11,971 ans, soit environ 3,000 ans de plus que ceux calculés auparavant par les modèles. L’aquifère superficiel présente des activités tritium plut?t élevées et variables (4 à 75 UT), démontrant l’existence d’une alimentation récente et d’un temps de résidence faible (<60 ans), ce qui concorde avec les études antérieures. Les signatures isotopiques indiquent une alimentation des eaux souterraines les plus profondes au cours d’épisodes climatiques plus froids et plus humides qu’actuellement, à la fin du Pléistocène et à l’Holocène. Les résultats suggèrent que des changements significatifs dans la planification des usages de l’eau sont nécessaires et urgents dans des perspectives d’exploitation durable.

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Resumen Se ha utilizado una combinación de indicadores isotópicos y químicos para caracterizar la precipitación, el agua superficial y el agua subterránea en la Cuenca del Río Heihe, China. Los datos químicos de aguas superficiales frente a las subterráneas no permiten diferenciar zonas geográficas y tipos químicos. La disolución de halita, sal de Glauber, yeso, dolomita y calcita determina la química de Na⁺, Cl⁻, Mg²⁺, Ca²⁺, y , pero otros procesos, como evaporación, intercambio de iones y precipitación influyen también en la composición del agua. La mayoría de las aguas subterráneas profundas confinadas no tienen Tritio y están menos mineralizados que el acuífero superficial. Los valores de radiocarbono en las aguas subterráneas más profundas oscilan entre 18.8 y 38.9 pmc, y el valor de 80 pmc representa probablemente el límite superior de la actividad inicial de ¹⁴C; proporcionando edades de aproximadamente 5,960–11,971 a?os BP, que son unos 3,000 a?os más antiguas de las calculadas mediante modelización en trabajos previos. El acuífero superficial tiene actividades de tritio bastante más altas y variables (4–75 UT), evidenciando una recarga reciente y unos tiempos de residencia bajos (<60 a?os), lo cual está en la línea de lo estimado en trabajos previos. Los datos isotópicos apuntan a la formación de aguas subterráneas más profundas en un clima más frío y húmedo durante el Pleistoceno superior y el Holoceno. Los resultados sugieren que se necesita hacer cambios significativos en la estrategia de uso del agua para alcanzar un desarrollo sostenible.

     

Hydrochemistry and isotope geochemistry as tools for groundwater hydrodynamic investigation in multilayer aquifers: a case study from Lomellina, Po plain, South-Western Lombardy, Italy

A multicriteria approach in studying hydrodynamics of a multilayer aquifer system has been used in the Lomellina region (Northern Italy). It involves the reconstruction of the hydrogeological framework coupled to the definition of the hydrochemical and isotopic features of the aquifers. A shallow phreatic aquifer, reaching depths of about 60–80 m from the surface, and deeper aquifers containing confined groundwater, were distinguished. Groundwater generally shows mineralisation decreasing with depth; dissolved ions depict calcium-bicarbonate hydrochemical facies and stable isotopes define the recharge mechanisms, the origin of groundwater, and the hydraulic confinement of deep aquifers. The phreatic aquifer is fed by local infiltration and by streams and irrigation channels. Tritium and Carbon-14 groundwater dating indicate long residence times (on the order of thousands of years) for confined aquifers. The confined aquifers show essentially passive hydrodynamic conditions and maintain a higher piezometric level than the phreatic aquifer. This inhibits the possibility of recent water penetrating far below the surface. The hydrogeological setting of the Lomellina region displays features which are common to other sectors of the Po plain. As a consequence, the results of this study, although conducted on a restricted area, are highly illustrative of groundwater hydrodynamics in large sedimentary aquifers.     

Hydrogeochemical and isotopic evolution of water in the Complexe Terminal aquifer in the Algerian Sahara

The hydrogeochemical and isotopic evolution of groundwaters in the Mio–Pliocene sands of the Complexe Terminal (CT) aquifer in central Algeria are described. The CT aquifer is located in the large sedimentary basin of the Great Oriental Erg. Down-gradient groundwater evolution is considered along the main representative aquifer cross section (south–north), from the southern recharge area (Tinrhert Plateau and Great Oriental Erg) over about 700 km. Groundwater mineralisation increases along the flow line, from 1.5 to 8 g l^?1, primarily as a result of dissolution of evaporite minerals, as shown by Br/Cl and strontium isotope ratios. Trends in both major and trace elements demonstrate a progressive evolution along the flow path. Redox reactions are important and the persistence of oxidising conditions favours the increase in some trace elements (e.g. Cr) and also NO₃ ^?, which reaches concentrations of 16.8 mg l^?1 NO₃-N. The range in ¹⁴C, 0–8.4 pmc in the deeper groundwaters, corresponds with late Pleistocene recharge, although there then follows a hiatus in the data with no results in the range 10–20 pmc, interpreted as a gap in recharge coincident with hyper-arid but cool conditions across the Sahara; groundwater in the range 24.7–38.9 pmc signifies a distinct period of Holocene recharge. All δ¹⁸O compositions are enriched relative to deuterium and are considered to be derived by evaporative enrichment from a parent rainfall around ?11‰ δ¹⁸O, signifying cooler conditions in the late Pleistocene and possibly heavy monsoon rains during the Holocene.     

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Magmatic garnet in the Triassic (215 Ma) Dehnow pluton of NE Iran and its petrogenetic significance

The Triassic Dehnow pluton of NE Iran is a garnet-bearing I-type calc-alkaline metaluminous diorite-tonalite-granodiorite intrusion. The parental magma formed as the result of partial melting of intermediate to felsic rocks in the lower crust. Petrological and geochemical evidence, which indicates a magmatic origin for the garnet, includes: large size (~10–20 mm) of crystals, absence of reaction rims, a distinct composition from garnet in adjacent metapelitic rocks, and similarity in the composition of mineral inclusions (biotite, hornblende) in the garnet and in the matrix. Absence of garnet-bearing enclaves in the pluton and lack of sillimanite (fibrolite) and cordierite inclusions in magmatic garnet suggests that the garnet was not produced by assimilation of meta-sedimentary country rocks. Also, the δ¹⁸O values of garnet in the pluton (8.3–8.7‰) are significantly lower than δ¹⁸O values of garnet in the metapelitic rocks (12.5–13.1‰). Amphibole-plagioclase and garnet-biotite thermometers indicate crystallization temperatures of 708°C and 790°C, respectively. A temperature of 692°C obtained by quartz-garnet oxygen isotope thermometry points to a closure temperature for oxygen diffusion in garnet. The composition of epidote (X_ep) and garnet (X_adr) indicates ~800°C for the crystallization temperature of these minerals. Elevated andradite content in the rims of garnet suggests that oxygen fugacity increased during crystallization.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].     

The use of environmental isotopic and hydrochemical tracers to characterize the functioning of karst systems in the Tlemcen Mountains,northwest Algeria

The functioning of karst systems in the Tlemcen Mountains, Algeria, was studied using environmental isotopic and chemical parameters. The weakly enriched values of ¹⁸O suggest a fast infiltration of water through the karst systems. The deuterium (²H) excess in groundwater and tritium (³H) in precipitation show that the region is subjected to Mediterranean and Atlantic influences with a predominance of the former. The isotopic gradient, in combination with topographic and geologic criteria, allows the recharge areas of the main karst systems to be estimated. The results of ¹³C, ¹⁴C and ³H analysis show that the majority of present waters come from perched systems and mixture waters influenced by three clusters (“ante-thermonuclear” waters, “thermonuclear” waters, and present waters) that generally emerge from semi-confined systems. The oldest waters are relatively rare and are stored in deeply confined systems. These results are consistent with the hydrochemical and the hydrogeological findings. The results have important implications in groundwater protection.     

Isotopes in the Hueco Bolson aquifer, Texas (USA) and Chihuahua (Mexico): local and general implications for recharge sources in alluvial basins

Stable isotope data for the Hueco Bolson aquifer (Texas, USA and Chihuahua, Mexico) distinguish four water types. Two types relate to recharge from the Rio Grande: pre-dam (pre-1916) river water with oxygen-18 and deuterium (δ¹⁸O, δD, ‰) from (?11.9, ?90) to (?10.1, ?82), contrasts with present-day river water (?8.5, ?74) to (?5.3, ?56). Pre-dam water is found beneath the Rio Grande floodplain and Ciudad Juárez, and is mixed with post-dam river water beneath the floodplain. Two other types relate to recharge of local precipitation; evidence of temporal change of precipitation isotopes is present in both types. Recharge from the Franklin and Organ Mountains plots between (?10.9, ?76) and (?8.5, ?60) on the global meteoric water line (GMWL), and is found along the western side of the Hueco Bolson, north of the Rio Grande. Recharge from the Diablo Plateau plots on an evaporation trend originating on the GMWL near (?8.5, ?58). This water is found in the southeastern Hueco Bolson, north of the river; evaporation may be related to slow recharge through fine-grained sediment. Pre-dam water, recognizable by isotope composition, provides information on groundwater residence times in this and other dammed river basins.     

Siderite mineralization of the Gemericum superunit (Western Carpathians, Slovakia): review and a revised genetic model

The Gemericum is a segment of the Variscan orogen subsequently deformed by the Alpine–Carpathian orogeny. The unit contains abundant siderite–sulphide and quartz–antimony veins together with stratabound siderite replacement deposits in limestones and stratiform sulphide mineralization in volcano-sedimentary sequences. The siderite–sulphide veins and siderite replacement deposits of the Gemericum represent one of the largest accumulations of siderite in the world, with about 160 million tonnes of mineable FeCO₃. More than 1200 steeply dipping hydrothermal veins are arranged in a regional tectonic and compositional pattern, reflecting the distribution of regional metamorphic zones. Siderite–sulphide veins are typically contained in low-grade (chlorite zone) sedimentary, volcano-sedimentary or volcanic Lower and Upper Paleozoic rocks. Quartz–antimony veins are hosted by higher-grade units (biotite zone). Siderite–sulphide veins are dominated by early siderite followed by a complex set of stages, including quartz–sulphide (chalcopyrite, tetrahedrite), barite, tourmaline–quartz, and sulphide-remobilization stages. The temporal evolution of these stages is difficult to study because of the widespread and repeated tectonic processes, within-vein replacement and recrystallization. Siderite–sulphide veins show considerable vertical (up to 1200 m) and lateral (up to 15 km) extent, and a thickness typically reaching several metres. Carbonate-replacement siderite deposits of the Gemericum are hosted by a Silurian limestone belt and are similar to stratabound siderite deposits of the Eastern Alps (e.g., Erzberg, Austria).Based on a review of geological, petrological and geochronological data for the Gemericum, and extensive stable and radiogenic isotope data and fluid inclusion data on hydrothermal minerals, the siderite–sulphide veins and siderite replacement deposits are classified as metamorphogenic in a broad sense. The deposits were formed during several stages of regional crustal-scale fluid flow. Isotope (S, C, Sr, Pb) fingerprinting identifies the metamorphosed rock complexes of the Gemericum as a source of most components of hydrothermal fluids. Fluid inclusion and stable isotope data evidence the participation of several contrasting fluid types, and the existence of contrasting P–T conditions during vein evolution. A high-δ¹⁸O, medium- to high-salinity, H₂O-type fluid is the most important component during siderite deposition, whereas H₂O–CO₂-type fluid inclusion containing dense liquid CO₂ and corresponding to minimal pressures between 1 and 3 kbar were found in a younger tourmaline–quartz stage. Younger quartz–ankerite(±siderite)–sulphide stages are characterized by high-salinity (17 to 35 wt.% NaCl equivalent) and low-temperature (T_h=90 to 180 °C) H₂O-type fluids.The vein deposits are interpreted as a result of multistage hydrothermal circulation, with Variscan and Alpine mineralization phases. Based on available indirect data, the most important mineralization phase was related to regional fluid flow during the uplift of a Variscan metamorphic core complex, producing siderite–sulphide (±barite) mineralization, while tourmaline–quartz stage and sulphide remobilization stages are related to Alpine processes. Two phases of vein evolution are evident from two groups of ⁸⁷Sr/⁸⁶Sr isotope ratios of Sr-rich, Rb-poor hydrothermal minerals: 0.71042–0.71541 in older barite and 0.7190–0.7220 in late-stage celestine and strontianite.     

Hydrochemical and isotope characteristics of spring water and travertine in the Baishuitai area (SW China) and their meaning for paleoenvironmental reconstruction

A method of combining hydrochemical data logging and in situ titrating with measurement of stable carbon and oxygen isotopes was used to reveal the hydrochemical and isotopic characteristics in the Baishuitai travertine scenic area of SW China. It was found that the travertine-forming springs have a very high concentration of calcium and bicarbonate, and accordingly very high CO₂ partial pressures, which are not likely to be produced by biological activity in soil alone. Further analysis of the stable carbon isotopes of the springs shows that the high pressure of CO₂ is mainly related to an endogenic CO₂ source. That means the Baishuitai travertine is endogenic in origin. This is contrast to the commonly accepted saying that the travertine deposition in this study simply is a product of warm and humid conditions in a karst ecological environment. Rapid CO₂ degassing from the water is triggered by the much higher partial pressures in water than that of the surrounding air. Consequently, as the waters flow downstream of the spring the pH increases, the waters become supersaturated with respect to calcite, and travertine is deposited. The preferential release of ¹²CO₂ to the atmosphere results in a progressive increase of travertine ¹³C downstream. This is concluded with a preliminary discussion of variation in travertine-forming water temperatures, according to differences in stable oxygen isotopic compositions of the travertine formed in different epochs at Baishuitai. It was found that the change in water temperature is as high as 13 °C, i.e., from 23 °C at about 2500 years b.p., to 10 °C at present. This may mainly reflect that the effect of geothermal source on water temperature is decreasing. The problems involved in paleoenvironmental reconstruction with endogene travertine are also discussed. They are the impacts of "dead carbon" in radiocarbon dating and the enrichment in ¹³C of travertine by endogenic CO₂ and degassing of CO₂ from water, which has to be considered in paleovegetation reconstruction when using ¹³C data of the endogene carbonate deposits.     

Spatio-temporal variation of stable isotopes of river waters, water source identification and water security in the Heishui Valley (China) during the dry-season

Spatial variations of δD and δ¹⁸O among seven tributaries and their water sources were investigated in the Heishui Valley of the Yangtze River, China during the dry-season in 2004. A one-way ANOVA (analysis of variation) test showed that both δD (p?18O (p?=?0.045) spatially varied among the seven tributaries. The plot of δ¹⁸O versus δD for the river water collected at different locations showed that isotopic fractionation occurred during the snow and glacial melting process. The depleted δ¹⁸O and δD in the tributary waters distributed above the local meteoric water line (LMWL) suggested that the glacial and early snowpack meltwater largely recharged these streams during the early spring. The meltwater was isotopically distinguishable from the precipitation and river water, which had been evaporated during warmer and drier times. If glaciers and snow accumulation diminish with future climate warming, the recharge of these tributaries’ baseflow will decline and the security of the water resource in this watershed will be threatened.     

Observation of isotopes in the water cycle—the Swiss National Network (NISOT)

The Swiss National Network for the Observation of Isotopes in the Water Cycle (NISOT) includes eleven precipitation, seven surface water (river) and three groundwater stations, where tritium, deuterium and oxygen-18 are monthly measured in composite samples. The network provides a good overview of the characteristic isotope signatures in recharge waters in Switzerland and of the relations between isotopes and altitude, orography and the amount of precipitation. Mixing of air water vapour and surface waters can be observed along a NW/SE cross section through the Alps. With increasing length of the data series, the network provides a valuable contribution for national and international scientific and practical applications in surface and subsurface hydrology, climatology and biology. The Swiss Geological Survey at the Federal Office for Water and Geology operates the isotope network within the legal framework of the Federal Law on the Protection of Waters and guarantees quality, access and distribution of the isotope data.     

Stable isotope study of cave percolation waters in subtropical Brazil: Implications for paleoclimate inferences from speleothems

We analyze the interannual monthly variability of oxygen isotope ratios in data from IAEA stations along the Atlantic coast of South America between 23° and 34° S to evaluate the influence of parameters such as temperature, rainfall amount and moisture source contribution on meteoric water recharging two karst systems in subtropical Brazil. In addition, a 2 year monitoring program performed on soil and cave drip and rimstone pool waters from sampling sites with contrasting discharge values and located at 100 and 300 m below the surface in the Santana Cave System (24°31′ S; 48°43′ W), is used to test the influence of hydrologic and geologic features on the temporal variations of seepage water δ¹⁸O.

Interannual monthly variations in δ¹⁸O of rainfall reflect primarily regional changes in moisture source contribution related to seasonal shifts in atmospheric circulation from a more monsoonal regime in summer (negative values of δ¹⁸O) to a more extratropical regime in winter (positive values of δ¹⁸O). Variations in groundwater δ¹⁸O indicate that the climatic signal of recent rainfall events is rapidly transmitted through the relatively deep karst aquifer to the cave drip waters, regardless of location of collection in the cave. In addition, the data also suggest that water replenishment in the system is triggered by the increase in hydraulic head during periods when recharge exceeds the storage capacity of the soil and epikarst reservoirs. Significant perturbations in the groundwater composition, characterized by more positive values of δ¹⁸O, are probably connected to an increased Atlantic moisture contribution associated with extratropical precipitation. This implies that the δ¹⁸O of speleothems from caves in this region may be a suitable proxy for studying tropical–extratropical interactions over South America, a feature that is intrinsically related to the global atmospheric circulation.     

Emarat carbonate-hosted Zn–Pb deposit, Markazi Province, Iran: A geological, mineralogical and isotopic (S, Pb) study

The Emarat deposit, with a total proved reserve of 10 Mt ore grading 6% Zn and 2.26% Pb, is one of the largest Zn–Pb deposits in the Malayer–Esfahan belt. The mineralization is stratabound and restricted to Early Cretaceous limestones and dolomites. The ore consists mainly of sphalerite and galena with small amounts of pyrite, chalcopyrite, calcite, quartz, and dolomite. Textural evidence shows that the ore has replaced the host rocks and thus is epigenetic.Sulfur isotopes indicate that the sulfur in sphalerite and galena has been derived from Cretaceous seawater through thermochemical sulfate reduction. Sulfur isotope compositions of four apparently coprecipitated sphalerite–galena pairs suggest their precipitation was under equilibrium conditions. The sulfur isotopic fractionation observed for the sphalerite–galena pairs corresponds to formation temperatures between 77 °C and 168 °C, which agree with homogenization temperatures of fluid inclusions.Lead-isotope studies indicate that the lead in galena has been derived from heterogeneous sources including orogenic and crustal reservoirs with high ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb ratios. Ages derived from the Pb-isotope model give meaningless ages, ranging from Early Carboniferous to future. It is probable that the Pb-isotope model ages that point to an earlier origin than the Early Cretaceous host rocks are derived from older reservoirs in the underlying Carboniferous or Jurassic units, either from the host rocks or from earlier-formed ore deposits within these units.This research and other available data show that the Emarat Zn–Pb deposit has many important features of Mississippi Valley-type (MVT) lead–zinc deposits and thus we argue that it is an MVT-type ore deposit.     

Indication of hydrogen and oxygen stable isotopes on the characteristics and circulation patterns of medium-low temperature geothermal resources in the Guanzhong Basin,China

Guanzhong Basin is a typical medium-low temperature geothermal field mainly controlled by geo-pressure in the west of China.The characteristics of hydrogen and oxygen isotopes were used to analyze the flow and storage modes of geothermal resources in the basin.In this paper,the basin was divided into six geotectonic units,where a total of 121 samples were collected from geothermal wells and surface water bodies for the analysis of hydrogen-oxygen isotopes.Analytical results show that the isotopic signatures of hydrogen and oxygen throughout Guanzhong Basin reveal a trend of gradual increase from the basin edge areas to the basin center.In terms of recharge systems,the area in the south edge belongs to the geothermal system of Qinling Mountain piedmont,while to the north of Weihe fault is the geothermal system of North mountain piedmont,where the atmospheric temperature is about 0.2℃-1.8℃in the recharge areas.The main factors that affect the geothermal waterδ18O drifting include the depth of geothermal reservoir and temperature of geothermal reservoir,lithological characteristics,water-rock interaction,geothermal reservoir environment and residence time.Theδ18O-δD relation shows that the main source is the meteoric water,together with some sedimentary water,but there are no deep magmatic water and mantle water which recharge the geothermal water in the basin.Through examining the distribution pattern of hydrogen-oxygen isotopic signatures,the groundwater circulation model of this basin can be divided into open circulation type,semi-open type,closed type and sedimentary type.This provides some important information for rational exploitation of the geothermal resources.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.