Hydrochemical and isotopic investigation of a sandstone aquifer groundwater in a semi arid region,El Ma El Abiod,Algeria

This work present results of the hydrochemical and isotopic studies on groundwater samples from the study area. Chemical and environmental isotope data are presented and discussed in terms of the origin of dissolved species and of groundwater. All of the investigated groundwater are categorized into two chemical types: low and relatively high mineralized waters type. Interpretation of chemical data, based on both thermodynamic calculations and stability diagrams, suggests that the chemical evolution of groundwater is primarily controlled by water-rock interactions. Interpretation of ¹⁸O and ²H suggests that the recharge of the investigated groundwater may result from differents mechanisms     

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.     

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].     

Fluoride contents in groundwaters and the main consumed foods (dates and tea) in Southern Algeria region

In the Algeria South, the dental fluorosis is a “silent” epidemic spreading within the populations. The present study was aimed to determine the fluoride content in water, dates and tea that are widely consumed. The results reveal that 35% of water wells had excessive fluoride levels (>1.5 mg/L). The eastern areas where dental decay is the most widespread pathology present the highest contents. Dates, tea and water are considerable sources of fluoride, with a daily contribution of 10, 20 and up to 70%, respectively. For these three sources, the daily intake of fluoride ingested by an adult exceeds the proposed safe threshold of 0.05–0.07 mg/kg day.     

Hydrochemical and stable isotope assessment of tailings pond leakage, Nickel Plate Mine, British Columbia

Received: 19 April 1999 · Accepted: 19 July 1999     

Hydrochemical and isotopical tracers in the lacustrine aquifer of the Cerro Prieto area, Baja California, México

A series of patterns in the chemical and isotopic composition of the groundwater of the Cerro Prieto area have been recognized. These patterns were used to define four hydrochemical and isotopical zones in the area. One of these areas located at the east side was found to be the source of recharge, while another in the central part is where an older aquifer exist in lacustrine deposits. The low permeability of the area causes the aquifer to act as an aquitard, which at least is partly surrounded by an interface zone where mixing of waters occurs. Tritium and radiocarbon method revealed that the aquitard is an isolate system whose residence time is of 32 ka.     

Quantification of karst aquifer discharge components during storm events through end-member mixing analysis using natural chemistry and stable isotopes as tracers

Karst aquifer components that contribute to the discharge of a water supply well in the Classical Karst (Kras) region (Italy/Slovenia) were quantitatively estimated during storm events. Results show that water released from storage within the epikarst may comprise as much as two-thirds of conduit flow in a karst aquifer following rainfall. Principal components analysis (PCA) and end-member mixing analysis (EMMA) were performed using major ion chemistry and the stable isotopes of water (δ¹⁸O, δ²H) and of dissolved inorganic carbon (δ¹³C_DIC) to estimate mixing proportions among three sources: (1) allogenic river recharge, (2) autogenic recharge, and (3) an anthropogenic component stored within the epikarst. The sinking river most influences the chemical composition of the water-supply well under low-flow conditions; however, this proportion changes rapidly during recharge events. Autogenic recharge water, released from shallow storage in the epikarst, displaces the river water and is observed at the well within hours after the onset of precipitation. The autogenic recharge end member is the second largest component of the well chemistry, and its contribution increases with higher flow. An anthropogenic component derived from epikarstic storage also impacts the well under conditions of elevated hydraulic head, accounting for the majority of the chemical response at the well during the wettest conditions.     

Hydrogeologic controls on groundwater recharge and salinization: a geochemical analysis of the northern Hueco Bolson aquifer, Texas, USA

Identification of hydrogeologic controls on groundwater flowpaths, recharge, and salinization is often critical to the management of limited arid groundwater resources. One approach to identifying these mechanisms is a combined analysis of hydrogeologic and hydrochemical data to develop a comprehensive conceptual model of a groundwater basin. To demonstrate this technique, water samples were collected from 33 discrete vertical zone test holes in the Hueco Bolson aquifer, located within the Trans-Pecos Texas region and the primary water resource for El Paso, Texas, USA and Juárez, Mexico. These samples were analyzed for a suite of geochemical tracers and the data evaluated in light of basin hydrogeology. On the basis of δ²H and δ¹⁸O data, two regional recharge sources were recognized, one originating from western mountain-fronts and one from through-flow of the adjacent Tularosa aquifer. Chloride concentrations were strongly correlated with lithologic formations and both Cl/Br and ³⁶Cl ratios suggested the primary chloride source is halite dissolution within a specific lithologic unit. In contrast, sulfur isotopes indicated that most sulfate originates from Tularosa basin Permian gypsum sources. These results yielded a more comprehensive conceptual model of the basin, which suggested that chloride salinization of wells is the result of upconing of waters from the Fort Hancock formation.     

A conceptual model for water resources circulation patterns in Andarokh-Kardeh region (NE,Iran)

Andarokh-Kardeh region is located northeast of Iran and provides notable part of potable water of Mashhad, the second most populated city of Iran with over 3 million inhabitants. Stable isotopes (¹⁸O, ²H and ¹³C), hydrodynamic, and hydrochemical indicators have been applied to evaluate water resources quality comprehensively and to present a hydrogeological conceptual model for the Andarokh-Kardeh region. Hydrochemical studies indicate that chemical rock weathering and ion exchange are the main factors controlling the quality of water in the region, while atmospheric (precipitation) as well as anthropogenic sources have no notable effect. Stable isotopes (¹⁸O and ²H) studies in surface and groundwater samples demonstrate enriched values in Kardeh Dam Reservoir (KDR) due to evaporation and also demonstrate that the interaction between KDR and downstream groundwater resources is negligible. The δ¹³C isotope and DIC and DOC concentrations indicate role of carbonate mineral dissolution from Mozdooran Formation, atmospheric and soil CO₂ and also the domination of C3 vegetation coverage in the study region. The developed conceptual model for Andarokh-Kardeh demonstrates different hydrogeological conditions during wet and dry periods, and highlights the main process which affect hydrogeology of the region. Water quality studies and the developed conceptual model demonstrate the main factors controlling water quality and the main hydrogeological characteristic of Andarokh-Kardeh region which can be used by water resources scientists for the future water management programmes.     

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.     

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.     

Multivariate analysis and geochemical investigations of groundwater in a semi-arid region,case of superficial aquifer in Ghriss Basin,Northwest Algeria

This study aims to investigate the hydrochemical characteristics of shallow aquifer in a semi-arid region situated in northwest Algeria, and to understand the major factors governing groundwater quality. The study area is suffering from recurring droughts, groundwater resource over-exploitation and groundwater quality degradation. The approach used is a combination of traditional hydrochemical analysis methods of multivariate statistical techniques, principal component analysis (PCA), and ratios of major ions, based on the data derived from 33 groundwater samples collected in February 2014. Results show that groundwater in the study area are highly mineralized and collectively has a high concentration of chloride (as Cl^?). The dominant water types are Na-Cl (27%), Mg-HCO₃ (24%) and Mg-Cl (24%). According to the (PCA) approach, salinization is the main process that controls the hydrochemical variability. The PCA analysis reveal the impact of anthropogenic factor especially the agricultural activities on the groundwater quality. The PCA highlighted two types of recharge: Superficial recharge from effective rainfall and excess irrigation water distinguished by the presence of nitrate and lateral recharge or vertical leakage from carbonate formations marked by the omnipresence of HCO₃^?. Additionally, three categories of samples were identified: (1) samples characterized by good water quality and receiving notable recharge from carbonate formations; (2) samples impacted by the natural salinization process; and (3) samples contaminated by anthropogenic activities. The major natural processes influencing water chemistry are the weathering of carbonate and silicate rocks, dissolution of evaporite as halite, evaporation and cation exchange. The study results can provide the basis for local decision makers to ensure the sustainable management of groundwater and the safety of drinking water.     

Hydrogeochemical and isotopic characterizations of an aquifer in the semi-arid region of the Mexican Highlands

This work addresses hydrogeochemical processes in shallow aquifers, represented by the Quaternary alluvial deposits, from a part of the semi-arid Mexican Highlands through the evaluations of physicochemical parameters as well as the δ¹⁸O and δ²H compositions of groundwater. Mifflin diagram separates the Na-bicarbonate, sulphate and mixed groundwater into one group showing interactions with volcanic lithology in the recharge zones and another group interacting with the evaporite rich sedimentary formation. In the Gibbs diagram, the samples with Cl^?/(Cl^? + HCO₃^?) < 0.4 showed higher influence of ion exchange and the samples with Cl^?/(Cl^? + HCO₃^?) > 0.4 showed higher effects of evaporation. All of them were oversaturated with carbonate minerals (i.e., calcite and dolomite) and unsaturated with evaporites (i.e., gypsum and halite). Evaporation (earlier stage) occurred before the water-rock interactions (later stage). Evolution occurs through three different routes such as up to 7.5‰ enrichment in δ¹⁸O caused by the infiltration with a certain delay and subsequently, the water-rock interaction became dominant. Ternary mixing models revealed dominant influence of local recharge (C₁) on the water system, contributing 70.4%. Water-rock interaction (C₃) with 18% and evaporation (C₂) with 11.6% had comparatively less influences. The presence of nitrate (2–60 mg/L) in the groundwater indicated variable degrees of anthropogenic pollution.     

Hydrochemical and isotopic characteristics of groundwater in the Souss Upstream Basin, southwestern Morocco

Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l⁻¹, and the following groundwater types are recognized: Ca²⁺–Mg²⁺–HCO₃⁻, Ca²⁺–Mg²⁺–SO₄²⁻ and Ca²⁺–Mg²⁺–Cl⁻. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ¹⁸O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ¹⁸O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.     

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.     

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.     

Geochemical heterogeneity and isotope geochemistry of natural attenuation processes in a gasoline-contaminated aquifer at the Hnevice site,Czech Republic

The geochemical processes, water–rock interactions and stable isotopes distribution (δ¹³C of DIC and δ¹⁸O and δ³⁴S of \({\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} \)) were investigated in the gasoline-contaminated aquifer at the Hnevice site, 50  km northwest of Prague, Czech Republic. Diesel, gasoline and oil leaks originate from a large fuel storage area causing heavy contamination of the saturated and unsaturated zones in an area of about 0.7  km². Groundwater investigations were conducted using five multilevel sampler wells with emphasis on redox parameters and degradation by-products and a solid-phase study focused on iron speciation and determination of principal and secondary minerals. Based on the study of groundwater and solid-phase geochemistry, four different geochemical zones were described. Zone I is thought to be background consisting of an aerobic aquifer and the absence of reduced species in significant concentrations. Zone II is situated in the plume core with methanogenic, sulphate and iron-reducing conditions accompanied by ankerite and kutnahorite precipitates and significant depletion of the oxidation capacity of the aquifer. Zone III is a mixing (corona) zone, situated at the fringe of the plume with high biodegradation rates and Fe(III)-precipitants. In zone IV, reoxidation of Fe(II) minerals (with e.g. the occurrence of psilomelane and cornelite) is typical.     

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.     

Stable isotope (C,O, S) systematics of the mercury mineralization at Idrija,Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the ¹³C and ¹⁸O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the ¹³C and ¹⁸O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (¹³C–4 and ¹⁸O+10), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The ³⁴S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The ³⁴S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from –19.1 to +22.8, and from –22.4 to +59.6, respectively, suggesting mixing of sulfur from different sources. The peak of ³⁴S values of cinnabar and pyrite close to 0 is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the ³⁴S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive ³⁴S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates.Editorial handling: P. Lattanzi     

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.