Field investigation of the natural attenuation and intrinsic biodegradation rates at an underground storage tank site

 Contamination of groundwater by petroleum-hydrocarbons is a widespread environmental problem. Natural attenuation is a passive remedial approach to degrade and dissipate contaminants in soil and groundwater. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is accomplished using the differences in total contaminant mass flux across two cross sections of the contaminant plume. The mass flux calculation shows that up to 88% of the dissolved BTEX (benzene, toluene, ethylbenzene, and xylene isomers) removal was observed by natural attenuation processes. The efficiency of intrinsic biodegradation was evaluated by the in situ tracer method. A first-order decay model was applied for the natural attenuation and intrinsic biodegradation rate calculation. Results reveal that intrinsic biodegradation process was the major cause of the BTEX reduction among the natural attenuation mechanisms, and iron reduction was the dominant biodegradation pattern within the plume. Approximately 87% of the BTEX removal was caused by intrinsic biodegradation processes. The calculated BTEX natural attenuation and intrinsic biodegradation rates were 0.24 and 0.16% l/day, respectively. Results suggest that natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the efficiency of the natural attenuation. Received: 6 December 1999 · Accepted: 11 July 2000     

Hydrogeochemistry of a deep gas-storage cavern,Czech Republic

Groundwater was occasionally found during the construction of a deep gas-storage cavern at approximately 1 km below land surface near Pribram, Czech Republic. The individual groundwater seeps, with a discharge not exceeding 0.01 l/s and T?=?23°C, were usually a strongly alkali natural solution with maximum pH values of 9.9 and TDS concentrations from 0.2 to 0.86 g/l; Na⁺, \({\text{HCO}}^{ - }_{3}\), and Cl^? ions were the major dissolved chemical constituents. Two main groundwater quality groups were defined: Na–Cl and Na–HCO₃. Based on the stable isotope (¹⁸O/¹⁶O, D/H), tritium and radiocarbon analyses, some groundwater originated from rainwater infiltrating during the Upper Pleistocene Epoch. Strontium in the groundwater of the crystalline aquifer was isotopically homogenous and equilibrates with strontium in the granite and granodiorite of the gas-storage cavern. Based on the information, the deep groundwater seeps were associated with slow or ‘stagnant’ groundwater circulation, without direct relation to the recent groundwater of faster circulation near the surface, which is periodically recharged by precipitation. The results of the water-quality monitoring of the deep groundwater seeps have been used in estimating the insulating properties of the neighboring rocks near the gas-storage cavern. This information will be important in the safe operation of the gas-storage cavern.     

Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

某石油类污染场地地下水石油烃生物降解的地球化学证据

生物降解地下水石油烃会改变地下水环境的水化学组成,因此可以通过分析污染晕中电子受体、生物降解代谢产物以及重要的地球化学参数量值变化获得生物降解的地球化学证据。本次在对某石油污染场地地质、水文地质条件、污染源污染方式调查基础上,根据地下水样测试结果,详细分析了地下水石油烃污染分布特征、污染晕中指示生物降解作用的电子受体、代谢产物以及重要地球化学参数的空间变化规律,研究结果表明:污染场地内存在氧还原、硝酸盐还原、硫酸盐还原等生物降解作用,其中硫酸盐还原是污染场地地下水石油烃生物降解的优势反应; 在沿地下水流向上,TPH浓度、HCO₃^-浓度和碱度逐渐降低,Eh、电子受体(DO、NO₃^-、SO₄^2-)浓度逐渐升高; 在垂直于地下水流向上,从中心向两侧各组分也呈相似的变化规律。     

Drainage and nutrient attenuation in a riparian interception-wetland: southern Minnesota,USA

Riparian wetlands have multiple source waters that require understanding to effectively manage water quantity and quality. Source waters were determined in an interception-wetland located a relatively flat clayey till terrain in southern Minnesota. Data loggers were used to measure precipitation, water stage from monitoring wells and a tile-drain outlet. Over 70 oxygen (δ¹⁸O), hydrogen (δD) and geochemical water samples were collected from seven locations over different seasons (9 events) from 1996 to 1999. Results indicate the dominant source water input to the wetland was drained shallow groundwater beneath intensively managed cropland (P = 0.000). Evapotranspiration was the dominant export pathway. Nitrate–nitrogen (NO₃-N) concentrations significantly decreased (P = 0.000) in the cattail-willow portion of the wetland. Total phosphorous (TP) concentrations were relatively high in the grass portion of the wetland (673 ± 549 μg L⁻¹), and relatively low in the cattail-willow portion of the wetland (139 ± 85 μg L⁻¹) because source waters were low in TP. Overall, the interception-wetland design limited out-of-bank flooding, yet allowed sufficient gradient between the cropland and the wetland outlet to minimize potential crop damage and provide hydraulic storage for nutrient attenuation.     

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.     

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.     

Assessment of the geological and hydrogeological environment at a site of government-level conflict in Incheon, Korea

 The natural environment of an environmental conflict site in Incheon, Korea was assessed with a focus on the hydrogeological environment. Residents had made claims against a company because of health problems, including skin tumors. More specifically, the residents suspected that their drinking groundwater had been contaminated by glass fibers which had caused the health problems. Air, soil, and groundwater samples were analyzed to estimate whether environmental pollution could have caused the problems claimed by the residents. No specific evidence was found from this study to support the groundwater contamination by glass fibers, but groundwater contamination by leaked fuel oils was confirmed in the course of evaluating the glass fiber problem. Received: 16 May 1997 · Accepted: 18 August 1997     

Recharge areas and geochemical evolution of groundwater in an alluvial aquifer system in the Sultanate of Oman

A regional hydrogeochemical model was developed to evaluate the geochemical evolution of different groundwaters in an alluvial aquifer system in the Interior of Oman. In combination with environmental isotopes the model is able to extract qualitative and quantitative information about recharge, groundwater flow paths and hydraulic connections between different aquifers. The main source of water to the alluvial aquifer along the flow paths of Wadi Abyadh and Wadi Muaydin in the piedmont is groundwater from the high-altitude areas of the Jabal Akhdar and local infiltration along the wadi channels. In contrast, the piedmont alluvial aquifer along Wadi Halfayn is primarily replenished by lateral recharge from the ophiolite foothills to the east besides smaller contributions from the Jabal Akhdar and local infiltration. Further down gradient in the Southern Alluvial Plain aquifer a significant source of recharge is direct infiltration of rain and surface runoff, originating from a moisture source that approaches Oman from the south. The model shows that the main geochemical evolution of the alluvial groundwaters occurs along the flow path from the piedmont to the Southern Alluvial Plain, where dedolomitization is responsible for the observed changes in the chemical and carbon isotope composition in these waters.

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Resumen Un modelo hidrogeoquímico regional fue desarrollado, para evaluar la evolución geoquímica de diferentes aguas subterráneas en un sistema acuífero aluvial ubicado en el interior de Omán. El modelo, en combinación con isótopos ambientales, es capaz de obtener información cualitativa y cuantitativa sobre recarga, direcciones de flujo de agua subterránea y sobre las conexiones hidráulicas entre diferentes acuíferos. La fuente principal de agua para el acuífero aluvial en el piedemonte son las aguas subterráneas, a lo largo de las direcciones de flujo del Wadi Abyadh y del Wadi Muaydin, desde las áreas de gran altura de Jabal Akhdar y como infiltración local a lo largo de los canales del wadi. En contraste, el acuífero aluvial del piedemonte a lo largo del Wadi Halfayn, esta alimentado principalmente por recarga lateral desde las partes bajas de las montañas de ofiolitas hacia el Este, además por pequeñas contribuciones desde el Jabal Akhdar e infiltración local. Siguiendo gradiente abajo en el acuífero de la Llanura Aluvial del Sur, allí tanto la infiltración directa de lluvia, como la escorrentía superficial constituyen fuentes significativas de recarga, las cuales se originan en una fuente de humedad que llega a Omán proveniente del Sur. El modelo muestra, que la evolución geoquímica principal de las aguas subterráneas en el aluvión, sucede a lo largo de la dirección de flujo, que va desde el piedemonte hacia la Llanura Aluvial Sur, en donde el proceso de des-dolomitización es el responsable de los cambios observados en la composición química y también del contenido de isótopos de carbono en estas aguas.

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Résumé On a développé un modèle régional hydrogéochimique pour évaluer lévolution géochimique des différentes eaux souterraines dans le système aquifère de lintérieur dOman. Avec la contribution des isotopes denvironnement, le modèle est capable de fournir des informations qualitatives et quantitatives sur la recharge, les directions découlement et sur les connections hydrauliques entre les différents aquifères du système. La source principale pour laquifère situé au long de la direction découlement des oueds de Abdyah et de Muaydin dans le piémont est leau souterraine provenant des zones de haute altitude de Jabal Akhbar ainsi que linfiltration locale au long des canaux de loued. Par contre, à part dune petite contribution provenant des infiltrations locaux et de Jabal Akhbar, l aquifère alluvial de Wadi Halfayan est en principal alimenté par la recharge latérale provenant des ophiolites situées dans la partie est. Les plus importantes sources de recharge dans laval de laquifère de la Plaine Alluviale sont linfiltration directe et le ruissellement provenant dune source dhumidité qui sapproche dOman par le sud. Le modèle montre que la principale évolution géochimique se produise au long de la direction découlement qui part de piémont de la Plaine Alluviale du Sud, où le procès de dédolomisation est responsable pour les changements observés dans la composition géochimique et en carbone des eaux.

     

Hydrogeochemistry and groundwater origin of the Basses-Laurentides sedimentary rock aquifer system, St. Lawrence Lowlands, Québec, Canada

A comprehensive hydrogeochemical study was carried out in the Paleozoic Basses-Laurentides sedimentary rock aquifer system in Québec over a 1500 km² study area. Groundwater samples were collected at 153 sites, characterizing all geological and hydrogeological units to a maximum depth of 140 m. Groundwater was analyzed for major, minor and trace inorganic constituents, stable isotopes δ ²H, δ ¹⁸O, and δ ¹³C of dissolved inorganic carbon (DIC), and some samples were analyzed for ³H, and ¹⁴C of DIC. The regional distribution of groundwater types shows that the hydrogeological conditions exert a dominant control on the major ions chemistry of groundwater. Preferential recharge areas are characterized by tritiated Ca-Mg-HCO₃ groundwater, and confined conditions by submodern Na-HCO₃ and Na-Cl groundwater types. Two groundwater end-members are identified in the aquifer system, modern meteoric water and Pleistocene Champlain Sea water. The region displays significant variations of groundwater geochemistry and quality controlled by glaciation, Champlain Sea invasion, lithological rock diversity, and flow system scales. This situation leads to varied groundwater types and origins within a restricted area.     

Groundwater flow and geochemistry in the lower reaches of the Yellow River: a case study in Shandang Province, China

Water samples were collected from the Yellow River and from wells for chemical and isotopic measurement in the counties of Yucheng and Qihe, to which 6–9×10⁸ m³ of water is diverted annually from the Yellow River. A zone of high electrical conductivity (EC) in groundwater corresponds well on the regional scale with a ridge in groundwater level, which is the main flow path through the region, but has a low gradient. The zone of highest EC along this ridge occurs at a position with the lowest ground altitude in the study area. The unique characteristic of the groundwater is the linear relationship among the principal anions as the result of mixing. The mixing effect is confirmed by its isotopic signature, which was then used to calculate the contributions from three sources: rainfall, old water, and diverted water with an average mixing rate of 18, 17, and 65%, respectively. As an indicator of water movement, Cl^– content varies across a wide range in the profile from 30–10 m with a maximum concentration at about 1.2 m depth. Concentrations are relatively stable at about 2 m, which is the average boundary of the saturated and unsaturated zone. The water from the Yellow River has proved to be dominant in mixing in the aquifer in terms of groundwater flow and geochemistry. Electronic Publication     

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.     

Characterizing vertical contaminant distribution in a thick unconfined aquifer,Hanford site,Washington, USA

Drilling-intensive aquifer characterization techniques have been used to obtain depth-discrete water samples from a thick, hydrogeologically continuous unconfined aquifer system; groundwater results indicate that carbon tetrachloride contamination is widespread and extends deeper and at concentrations much higher than detected in monitoring networks at the water table. Carbon tetrachloride, a legacy waste, was used in the plutonium extraction process at the Hanford site in south-central Washington State. Vertical, depth-discrete groundwater samples were collected during well drilling throughout a 28-km² region to determine the concentration of carbon tetrachloride present as a dissolved phase in the aquifer. Results indicate that high concentrations of carbon tetrachloride, three orders of magnitude above the allowable regulatory limit, are present at depths greater than 25 m beneath the water table. In support of future efforts to remediate the carbon tetrachloride contamination, it is imperative to locate the remaining chemical inventory, determine the vertical as well as the lateral distribution of this contaminant and its physical form. Depth-discrete aquifer characterization throughout the uppermost-unconfined aquifer system is providing this information and improving the understanding of the contaminant distribution and the hydrogeologic framework through which it moves.

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Well site conditions associated with nitrate contamination in a multilayer semiconfined aquifer of Buenos Aires,Argentina

A stepwise logistic regression (LR) model was generated to evaluate the association between contamination of groundwater by nitrates with several risk factors such as soil types, farm facilities and practises, and well characteristics. The odds ratio was calculated to estimate the degree of impact that the associated variables had on the risk of contamination in a semiconfined multilayer aquifer underlying rural areas of Buenos Aires, Argentina. Duplicate farm groundwater samples (n = 160) were taken and nitrate was analyzed. Data, involving various farm factors, was gathered via two questionnaires concerning farm’s general and productive aspects, and well characteristics. Statistical tests were run between nitrates and each variable present in the survey. A 96.25% of the samples presented detectable nitrate levels, 40.91% of which had more than 45 ppm nitrates. The final LR model involved five of the variables under study: well age, soil permeability, depth of water table, location, and distance from well to contamination sources. Cross validation proved to be a good estimator of nitrate water contamination. Suspicions about how these characteristics influence groundwater contamination by nitrates were confirmed, and as these five factors represent a higher risk for this type of aquifer, their proper management may contribute to a better resource protection.     

Carbon, oxygen, and strontium isotope geochemistry of carbonate rocks of the upper Miocene Kudankulam Formation, southern India: Implications for paleoenvironment and diagenesis

The carbon, oxygen, and strontium isotope compositions of carbonate rocks from the upper Miocene Kudankulam Formation, southern India, were measured to understand palaeoenvironment and carbonate diagenesis of this formation. Both carbon and oxygen isotope ratios of various carbonate phases including whole rocks, ooids, molluscan mold-fill and sparry pore-fill calcite cements are depleted in ¹⁸O and ¹³C compared to those of contemporaneous seawater, indicating that the Kudankulam carbonates underwent extensive meteoric diagenesis. Based on δ¹³C and δ¹⁸O values for sparry calcite cements (pore-fill and molluscan mold-fill) formed in the meteoric diagenetic realm (δ¹³C from −7.8‰ to −6.0‰ and −9.0‰ to −7.0‰; δ¹⁸O from −9.2‰ to −6.5‰ and −9.4‰ to −2.6‰, respectively), it is interpreted that the diagenetic system was open and was proximal to the vadose water recharge zone. The negative δ¹⁸O values of various carbonate components (about −9.4‰ to −4.1‰ for whole rocks; about −8.4‰ to −2.6‰ for ooids) suggest that during the late Miocene the paleoclimate of the study area was humid, unlike today, probably due to the intense Indian monsoon system. The carbon isotope compositions (−7.9‰ to −3.6‰ for whole rocks; −4.9‰ to −1.5‰ for ooids) are consistent with the interpretation that the paleo-ecosystem comprised a significant proportion of C₄ type plants, supporting a scenario of expansion of C₄ plants during the late Miocene in the Indian subcontinent as far south as the southern tip of India. The ⁸⁷Sr/⁸⁶Sr ratios of the Kudankulam carbonates (0.70920 to 0.72130) are much greater than those of the contemporaneous or modern seawater (between 0.7089 and 0.7091) and show a general decrease up-sequence. Such high Sr isotope ratios indicate significant radiogenic ⁸⁷Sr influx to the system from the Archean rocks exposed in the drainage area, implying that the deep-seated Archean rocks were already exposed in southern India by the late Miocene.     

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     

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.     

Environmental isotopic study on the recharge and residence time of groundwater in the Heihe River Basin, northwestern China

The recharge and origin of groundwater and its residence time were studied using environmental isotopic measurements in samples from the Heihe River Basin, China. δ¹⁸O and δD values of both river water and groundwater were within the same ranges as those found in the alluvial fan zone, and lay slightly above the local meteoric water line (δD=6.87δ¹⁸O+3.54). This finding indicated that mountain rivers substantially and rapidly contribute to the water resources in the southern and northern sub-basins. δ¹⁸O and δD values of groundwater in the unconfined aquifers of these sub-basins were close to each other. There was evidence of enrichment of heavy isotopes in groundwater due to evaporation. The most pronounced increase in the δ¹⁸O value occurred in agricultural areas, reflecting the admixture of irrigation return flow. Tritium results in groundwater samples from the unconfined aquifers gave evidence for ongoing recharge, with mean residence times of: less than 36 years in the alluvial fan zone; about 12–16 years in agricultural areas; and about 26 years in the Ejina oasis. In contrast, groundwater in the confined aquifers had ¹⁴C ages between 0 and 10 ka BP.     

Movement of water through the thick unsaturated zone underlying Oro Grande and Sheep Creek Washes in the western Mojave Desert,USA

Previous studies indicate that a small quantity of recharge occurs from infiltration of streamflow in intermittent streams in the upper Mojave River basin, in the western Mojave Desert, near Victorville, California. Chloride, tritium, and stable isotope data collected in the unsaturated zone between 1994 and 1998 from boreholes drilled in Oro Grande and Sheep Creek Washes indicate that infiltration of streamflow occurs to depths below the root zone, and presumably to the water table, along much of Oro Grande Wash and near the mountain front along Sheep Creek Wash. Differences in infiltration at sites along each wash are the result of hydrologic variables such as proximity to the mountain front, quantity of streamflow, and texture of the subsurface deposits. Differences in infiltration between the washes are the result of large-scale geomorphic processes. For example, Oro Grande wash is incised into the Victorville fan and infiltration has occurred at approximately the same location over recent geologic time. In contrast, Sheep Creek Wash overlies an active alluvial fan and the stream channel can move across the fan surface through time. Infiltration does not occur to depths below the root zone at control sites outside of the washes. Electronic Publication