Environmental tracers as indicators of karst conduits in groundwater in South Dakota,USA

Environmental tracers sampled from the carbonate Madison aquifer on the eastern flank of the Black Hills, South Dakota, USA indicated the approximate locations of four major karst conduits. Contamination issues are a major concern because these conduits are characterized by direct connections to sinking streams, high groundwater velocities, and proximity to public water supplies. Objectives of the study were to estimate approximate conduit locations and assess possible anthropogenic influences associated with conduits. Anomalies of young groundwater based on chlorofluorocarbons (CFCs), tritium, and electrical conductivity (EC) indicated fast moving, focused flow and thus the likely presence of conduits. δ¹⁸O was useful for determining sources of recharge for each conduit, and nitrate was a useful tracer for assessing flow paths for anthropogenic influences. Two of the four conduits terminate at or near a large spring complex. CFC apparent ages ranged from 15 years near conduits to >50 years in other areas. Nitrate-N concentrations >0.4 mg/L in groundwater were associated with each of the four conduits compared with concentrations ranging from <0.1 to 0.4 mg/L in other areas. These higher nitrate-N concentrations probably do not result from sinking streams but rather from other areas of infiltration.     

Application of environmental groundwater tracers at the Sulphur Bank Mercury Mine, California, USA

Boron, chloride, sulfate, δD, δ¹⁸O, and ³H concentrations in surface water and groundwater samples from the Sulphur Bank Mercury Mine (SBMM), California, USA were used to examine geochemical processes and provide constraints on evaporation and groundwater flow. SBMM is an abandoned sulfur and mercury mine with an underlying hydrothermal system, adjacent to Clear Lake, California. Results for non-³H tracers (i.e., boron, chloride, sulfate, δD, and δ¹⁸O) identify contributions from six water types at SBMM. Processes including evaporation, mixing, hydrothermal water input and possible isotopic exchange with hydrothermal gases are also discerned. Tritium data indicate that hydrothermal waters and other deep groundwaters are likely pre-bomb (before ~1952) in age while most other waters were recharged after ~1990. A boron-based steady-state reservoir model of the Herman Impoundment pit lake indicates that 71–79% of its input is from meteoric water with the remainder from hydrothermal contributions. Results for groundwater samples from six shallow wells over a 6–month period for δD and δ¹⁸O suggests that water from Herman Impoundment is diluted another 3% to more than 40% by infiltrating meteoric water, as it leaves the site. Results for this investigation show that environmental tracers are an effective tool to understand the SBMM hydrogeologic regime.

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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Résumé Les concentrations en bore, chlorure, sulfate, δD, δ¹⁸O, et ³H d’échantillons d’eaux de surface et souterraine prélevés dans le banc de soufre de la mine de mercure (SBMM en anglais) en Californie, USA, ont été utilisées pour étudier les processus géochimiques et pour fournir des contraintes à l’évaporation et à l’écoulement des eaux souterraines. La SBMM est une mine de soufre et de mercure abandonnée, adjacente au lac Clear en Californie et sous laquelle se trouve un système hydrothermal.Les résultats des traceurs autres que le tritium (bore, chlorure, sulfate, δD, et δ¹⁸O) ont permis d’identifier des contributions de six types d’eaux à SBMM. Des processus tels que l’évaporation, le mélange, l’entrée d’eau hydrothermale et de possibles échanges isotopiques avec des gaz hydrothermaux ont également été identifiés. Les données de tritium montrent que les eaux hydrothermales et d’autres eaux profondes sont probablement d’age antérieure à la bombe (avant ~1952), alors que la plupart des autres eaux sont issues de la recharge après ~1990. Un modèle de réservoir représentant le lac situé dans la partie Herman Impoundment de l’ancienne mine, en régime permanent et basé sur le bore, montre que 71–79% de l’eau provient des précipitations, le reste provenant de contributions hydrothermales. Les résultats de δD et δ¹⁸O pour des échantillons d’eau souterraine de six puits peu profonds sur une période de 6 mois suggèrent que l’eau de Hermann Impoundment est encore diluée entre 3% jusqu’à plus de 40% lorsqu’elle quitte le site du fait de l’infiltration d’eau météorique. Les résultats de cette étude montrent que les traceurs environnementaux constituent un outil efficace pour comprendre le régime hydrogéologique de la SBMM.

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Resumen Se han utilizado datos de concentraciones de boro, cloruros, sulfatos, δD, δ¹⁸O, y ³H en muestras de aguas superficiales y subterráneas procedentes de la Mina de Mercurio Sulphur Bank (SBMM), California, USA, para estudiar los procesos geoquímicos y caracterizar la evaporación y el flujo del agua subterránea. SBMM es una mina abandonada de azufre y mercurio con un sistema hidrotermal subyacente, cercano al Lago Clear, California.Los resultados de los trazadores que no son ³H (por ejemplo, boro, cloruros, sulfatos δD, y δ¹⁸O) identifican las contribuciones de seis tipos de agua en la SBMM. Se han identificado diversos procesos, como evaporación, mezcla, entrada de agua hidrotermal y la posibilidad de intercambios isotópicos con gases hidrotermales. Los datos de tritio indican que las aguas hidrotermales y otras aguas subterráneas profundas son probablemente pre-bombas (previas a ~1952) en edad mientras que la mayoría de las otras aguas se han recargado después de ~1990. Un modelo estacionario basado en el boro de la fosa del lago Herman Impoundment indica que el 71–79% de su entrada procede de agua meteórica con restos de contribución hidrotermal. Los resultados para las muestras de aguas subterráneas procedentes de seis pozos superficiales en un periodo de 6 meses para δD y δ¹⁸O sugieren que el agua procedente de Herman Impoundment se diluye en otro 3% hasta más del 40% debido a la infiltración de agua meteórica., que sale del sitio. Los resultados de esta investigación muestran que los trazadores ambientales son una herramienta efectiva para entender el régimen hidrogeológico de la SBMM.

     

Hydrogeochemistry and isotope analyses used to determine groundwater recharge and flow in low-gradient catchments of the province of Buenos Aires,Argentina

The region known as Pampa Plain, in Argentina, is a vast area characterized by slopes of less than 0.05%. The surface sediment is silty sand, mainly Aeolian, referred to as Pampean Loess, which is a phreatic aquifer unit of utmost importance for the water supply of the region. On account of the slight gradient, hydrogeological analyses using only hydraulic measurements are difficult to perform, often leading to confusing results. Thus, the study presented relies on hydrochemical modeling and isotopic determinations as well. The study area comprises three catchments in the inter-mountainous area corresponding to El Moro, Tamangueyú and Seco creeks, and covering 2,570 km² in the province of Buenos Aires. Measurements of piezometric levels and samples of groundwater, surface water and rainwater were carried out between January and March 2005. Major ion results were analyzed by means of hydrochemical graphs and hydrogeochemical modelling using NETPATH. The resulting data show that it is possible to identify local changes in recharge, flow direction and stream/groundwater relationship by using hydrochemical and isotopic information, which may become a useful and more precise tool for the study of particularly flat landscapes.     

Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

Stable isotope study of carbonate-cemented rocks from the Pobitite Kamani area,north-eastern Bulgaria

The Precipitation of carbonate cements in the Pobitite Kamani area (Lower Eocene) began during early diagenesis of sediments. There is evidence, however, that calcite is still forming today.The negative ¹³C values to –29.2 suggest that the carbonate formed during degradation of ¹²C-enriched organic matter (perhaps partly from oxidation of methane). The ¹⁸O values of –0.9 to –1.6 reflect the marine origin of the early diagenetic carbonate cements. Most of the carbonates, however, formed during late diagenesis (at approximately 1300 m burial depth) and/or recently (after uplift) from percolating groundwaters. These carbonates have an isotopic composition characteristic of carbonates which precipitated from meteoric waters under normal sedimentary temperatures in isotopic equilibrium with ¹²C-enriched soil carbon dioxide.     

Geochronology and geochemistry of eclogites from the Mariánské Lázně Complex,Czech Republic: Implications for Variscan orogenesis

The Mariánské Lázn complex (MLC) is located in the Bohemian Massif along the north-western margin of the Teplá-Barrandian microplate and consists of metagabbro, amphibolite and eclogite, with subordinate amounts of serpentinite, felsic gneiss and calcsilicate rocks. The MLC is interpreted as a metaophiolite complex that marks the suture zone between the Saxothuringian rocks to the north-west and the Teplá-Barrandian microplate to the south-east. Sm-Nd geochronology of garnet-omphacite pairs from two eclogite samples yields ages of 377±7, and 367±4 Ma. Samples of eclogite and amphibolite do not define a whole rock Sm-Nd isochron, even though there is a large range in Sm/Nd ratio, implying that the suite of samples may not be cogenetic. Eclogites do not have correlated _Nd values and initial ⁸⁷Sr/⁸⁶Sr ratios. Five of the eight eclogite samples have high _Nd values (+10.2 to +7.1) consistent with derivation from a MORB-like source, but variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7059) which probably reflect hydrothermal seawater alteration. Three other eclogite samples have lower _Nd values (+ 5.4 to –0.8) and widely variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7096). Such low _Nd values are inconsistent with derivation from a MORB, source and may reflect a subduction or oceanic island basalt component in their source. The MLC is an important petrotectonic element in the Bohemian Massif, providing evidence for Cambro-Ordovician formation of oceanic crust and interaction with seawater, Late Devonian (Frasnian-Famennian) high- and medium-pressure metamorphism related to closure of a Saxothuringian ocean basin, Early Carboniferous (Viséan) thrusting of the Teplá terrane over Saxothuringian rocks and Late Viséan extension.     

The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Can stable isotopes be used to monitor landfill leachate impact on surface waters?

Bacterially mediated methanogenesis in municipal solid waste landfills has been shown to cause an enrichment of carbon stable isotope ratios of dissolved inorganic carbon and hydrogen stable isotope ratios of water in landfill leachate. In the present study, we investigate the universality of this enrichment in leachate obtained from four diverse landfill sites in New Zealand. At each site, surface water samples upstream and downstream of landfills were analysed to examine the applicability of stable isotope ratios as a tool for monitoring leachate contamination in landfill-associated streams. The design of leachate collection systems, operational history, and landfill location appeared to strongly influence leachate isotopic values and the effectiveness of isotope ratios as an environmental monitoring tool for surface water.