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Lima, G. F. C., Filho, C. A. de C., Ferreira, V. G., Lima, J. da S. D., Marques, E. D., Minardi, P. S. P., et al. (2023). Establishing a water baseline for the unconventional gas industry: A multiple environmental isotopes assessment (18O, 2H, 3H, 13C, and 14C) of surface and groundwater in the São Francisco Basin, Brazil. Applied Geochemistry, 159, 105818.
Abstract: Unconventional hydrocarbon production has become the target of an intensive environmental debate due to the risks it poses to water resources. Fracking, while enabling the extraction of oil and gas from ultra-low permeability reservoirs, also possesses the risk of polluting water systems through failures from hydraulic fracturing and its associated procedures. The need to foster national industrial development with a transitional energy matrix has led Brazil to discuss the environmental suitability before producing its large unconventional reserves. Many studies have highlighted the need for a robust environmental characterization before the development of the unconventional industry. In this sense, multiple environmental isotopes may work as a proxy for identifying water contamination right from the early stages. Environmental isotopes may also be applied to enhance the understanding of the natural geochemical processes intrinsic to a given area. This study presents an environmental isotopes baseline for the groundwater and riverine water systems within the São Francisco Basin, a proven tight gas reservoir in Brazil, in a pre-operational context. δ18O, δ2H, 3H, δ13C, and Δ14C were evaluated in three different seasons in groundwater and surface water samples, along with other auxiliary parameters such as physical-chemical parameters (in situ), major ions, and d-excess. The δ2H and δ18O in surface water shows an upstream → downstream enrichment trend, with some variations suggesting baseflow interactions in the surface water systems. An evaporation line for the study area was defined as δ2H = 4.6903 δ18O + 10.362. δ13C indicates a mutual dissolution of silicates and carbonates in the groundwater system and suggests a group of samples highly related to the recharge areas. Groundwater dating denotes the Serra da Saudade Formation as a modern fractured aquifer with a strong recharge capacity. These findings support stakeholders in environmental monitoring and management of the unconventional gas industry.
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Smedley, P. L., & Kinniburgh, D. G. (2023). Uranium in natural waters and the environment: Distribution, speciation and impact. Applied Geochemistry, 148, 105534.
Abstract: The concentrations of U in natural waters are usually low, being typically less than 4 μg/L in river water, around 3.3 μg/L in open seawater, and usually less than 5 μg/L in groundwater. Higher concentrations can occur in both surface water and groundwater and the range spans some six orders of magnitude, with extremes in the mg/L range. However, such extremes in surface water are rare and linked to localized mineralization or evaporation in alkaline lakes. High concentrations in groundwater, substantially above the WHO provisional guideline value for U in drinking water of 30 μg/L, are associated most strongly with (i) granitic and felsic volcanic aquifers, (ii) continental sandstone aquifers especially in alluvial plains and (iii) areas of U mineralization. High-U groundwater provinces are more common in arid and semi-arid terrains where evaporation is an additional factor involved in concentrating U and other solutes. Examples of granitic and felsic volcanic terrains with documented high U concentrations include several parts of peninsular India, eastern USA, Canada, South Korea, southern Finland, Norway, Switzerland and Burundi. Examples of continental sandstone aquifers include the alluvial plains of the Indo-Gangetic Basin of India and Pakistan, the Central Valley, High Plains, Carson Desert, Española Basin and Edwards-Trinity aquifers of the USA, Datong Basin, China, parts of Iraq and the loess of the Chaco-Pampean Plain, Argentina. Many of these plains host eroded deposits of granitic and felsic volcanic precursors which likely act as primary sources of U. Numerous examples exist of groundwater impacted by U mineralization, often accompanied by mining, including locations in USA, Australia, Brazil, Canada, Portugal, China, Egypt and Germany. These may host high to extreme concentrations of U but are typically of localized extent. The overarching mechanisms of U mobilization in water are now well-established and depend broadly on redox conditions, pH and solute chemistry, which are shaped by the geological conditions outlined above. Uranium is recognized to be mobile in its oxic, U(VI) state, at neutral to alkaline pH (7–9) and is aided by the formation of stable U–CO3(±Ca, Mg) complexes. In such oxic and alkaline conditions, U commonly covaries with other similarly controlled anions and oxyanions such as F, As, V and Mo. Uranium is also mobile at acidic pH (2–4), principally as the uranyl cation UO22+. Mobility in U mineralized areas may therefore occur in neutral to alkaline conditions or in conditions with acid drainage, depending on the local occurrence and capacity for pH buffering by carbonate minerals. In groundwater, mobilization has also been observed in mildly (Mn-) reducing conditions. Uranium is immobile in more strongly (Fe-, SO4-) reducing conditions as it is reduced to U(IV) and is either precipitated as a crystalline or ‘non-crystalline’ form of UO2 or is sorbed to mineral surfaces. A more detailed understanding of U chemistry in the natural environment is challenging because of the large number of complexes formed, the strong binding to oxides and humic substances and their interactions, including ternary oxide-humic-U interactions. Improved quantification of these interactions will require updating of the commonly-used speciation software and databases to include the most recent developments in surface complexation models. Also, given their important role in maintaining low U concentrations in many natural waters, the nature and solubility of the amorphous or non-crystalline forms of UO2 that result from microbial reduction of U(VI) need improved quantification. Even where high-U groundwater exists, percentage exceedances of the WHO guideline value are variable and often small. More rigorous testing programmes to establish usable sources are therefore warranted in such vulnerable aquifers. As drinking-water regulation for U is a relatively recent introduction in many countries (e.g. the European Union), testing is not yet routine or established and data are still relatively limited. Acquisition of more data will establish whether analogous aquifers elsewhere in the world have similar patterns of aqueous U distribution. In the high-U groundwater regions that have been recognized so far, the general absence of evidence for clinical health symptoms is a positive finding and tempers the scale of public health concern, though it also highlights a need for continued investigation.
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Qiu, W., Yang, Y., Song, J., Que, W., Liu, Z., Weng, H., et al. (2023). What chemical reaction dominates the CO2 and O2 in-situ uranium leaching?: Insights from a three-dimensional multicomponent reactive transport model at the field scale. Applied Geochemistry, 148, 105522.
Abstract: The complex behavior of uranium in recovery is mostly driven by water-rock interactions following lixiviant injection into ore-bearing aquifers. Significant challenges exist in exploring the geochemical processes responsible for uranium release and mobilization. Herein this study provides an illustration of a ten-year field scale CO2 and O2 in-situ leaching (ISL) process at a typical sandstone-hosted uranium deposit in northern China. We also conducte a three-dimensional (3-D) multicomponent reactive transport model to assess the effects of potential chemical reactions on uranium recovery, in particular, to focus on the role of sulfide mineral pyrite (FeS2). Numerical simulations are performed considering three potential ISL reaction pathways to determine the relative contributions to uranium release, and the results indicate that bicarbonate promotes the oxidative dissolution of uranium-bearing minerals and further accelerates the uranium leaching in a neutral geochemical system. Moreover, the presence of FeS2 exerts a strong competitive role in the uranium-bearing mineral dissolution by increasing oxygen consumption, favoring the formation of iron oxyhydroxide, and therefore causing an associated decrease in uranium recovery rates. The simulation model demonstrates that dissolution of carbonate neutralizes acidic water generated from pyrite oxidation and aqueous CO2 dissociation. In addition, the cation concentrations (i.e., Ca and Mg) are increasing in the pregnant solutions, showing that the recycling of lixiviants and kinetic dissolution of carbonate generates a larger number of dissolved Ca and Mg and inevitably triggers the secondary dolomite mineral precipitation. The findings improve our fundamental understanding of the geochemical processes in a long-term uranium ISL system and provide important environmental implications for the optimal design of uranium recovery, remediation, and risk exposure assessment.
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Lapworth, D. J., Brauns, B., Chattopadhyay, S., Gooddy, D. C., Loveless, S. E., MacDonald, A. M., et al. (2021). Elevated uranium in drinking water sources in basement aquifers of southern India. Applied Geochemistry, 133, 105092.
Abstract: Groundwater resources in the crystalline basement complex of India are crucial for supplying drinking water in both rural and urban settings. Groundwater depletion is recognised as a challenge across parts of India due to over-abstraction, but groundwater quality constraints are perhaps even more widespread and often overlooked at the local scale. Uranium contamination in basement aquifers has been reported in many parts of India, locally exceeding WHO drinking water guideline values of 30 μg/L and posing a potential health risk. In this study 130 water samples were collected across three crystalline basement catchments to assess hydrochemical, geological and anthropogenic controls on uranium mobility and occurrence in drinking water sources. Groundwaters with uranium concentrations exceeding 30 μg/L were found in all three study catchments (30% of samples overall), with concentrations up to 589 μg/L detected. There appears to be a geological control on the occurrence of uranium in groundwater with the granitic gneiss of the Halli and Bengaluru study areas having higher mean uranium concentrations (51 and 68 μg/L respectively) compared to the sheared gneiss of the Berambadi catchment (6.4 μg/L). Uranium – nitrate relationships indicate that fertiliser sources are not a major control on uranium occurrence in these case studies which include two catchments with a long legacy of intense agricultural land use. Geochemical modelling confirmed uranium speciation was dominated by uranyl carbonate species, particularly ternary complexes with calcium, consistent with uranium mobility being affected by redox controls and the presence of carbonates. Urban leakage in Bengaluru led to low pH and low bicarbonate groundwater hydrochemistry, reducing uranium mobility and altering uranium speciation. Since the majority of inhabitants in Karnataka depend on groundwater abstraction from basement aquifers for drinking water and domestic use, exposure to elevated uranium is a public health concern. Improved monitoring, understanding and treatment of high uranium drinking water sources in this region is essential to safeguard public health.
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Heine, F., & Einsiedl, F. (2021). Groundwater dating with dissolved organic radiocarbon: A promising approach in carbonate aquifers. Applied Geochemistry, 125, 104827.
Abstract: A complete hydrogeological understanding of the deep Upper Jurassic carbonate aquifer in the South German Molasse Basin is essential for the future development of this important drinking water resource and geothermally used system. Water chemistry data, δ13CDIC, 14C of the dissolved inorganic carbon (14CDIC) and stable water isotope (δ18O and δD) measurements have been used to evaluate a promising groundwater dating approach with 14C of dissolved organic carbon (14CDOC). The pre-concentration of dissolved organic matter (DOM) was performed by the easy applicable solid phase extraction (SPE) with a styrene-divinylbenzene copolymer sorbent (PPL). Based on the sampling campaign of seven groundwater wells conducted between 2017 and 2019, it was shown that the groundwater is mainly of Ca–HCO3 type with some evidence of ion exchange between Ca2+ and Na+ at two of the investigated wells. The δD values ranged from −89.4‰ to −70.9‰ while δ18O values varied between −12.5‰ and −9.8‰. The obtained stable water isotope signatures indicated that the groundwater is of meteoric origin and was recharged during warm climate (Holocene), intermediate climate and cold climate (Pleistocene) infiltration conditions. The measured 14CDOC activities varied from 5.7 pmC to 51.1 pmC and the calculated piston-flow water ages (ORAs) ranged from 4200 years to 25,248 years using an initial 14C0DOC of 85 pmC. The calculated ORAs showed a very good correlation to the infiltration temperature-sensitive δ18O values which were affirmed with noble gas infiltration temperatures for two wells after Weise et al. (1991) and were also in good accordance with the atmospheric temperature record of the northern hemisphere from Dokken et al. (2015). The results reflect a consistent hydrogeological picture of the carbonate aquifer, which also supports the applicability of the SPE-PPL method for 14CDOC dating in groundwater with a low DOC content (<1 mg/l). In contrast, 14CDIC activities of 1.4 pmC to 21.3 pmC led to geochemically corrected piston-flow ages between 8057 years and >30,000 years and generally to an overestimation of the apparent water ages. This study gives insights into the promising approach of 14CDOC groundwater dating in carbonate aquifers with low DOC contents and allows future sustainable groundwater resource management of the investigated aquifer system.
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Christofi, C., Bruggeman, A., Külls, C., & Constantinou, C. (2020). Isotope hydrology and hydrogeochemical modeling of Troodos Fractured Aquifer, Cyprus: The development of hydrogeological descriptions of observed water types. Applied Geochemistry, 123, 104780.
Abstract: The origin of groundwater recharge and subsequent flow paths are often difficult to establish in fractured, multi-lithological, and highly compartmentalized aquifers such as the Troodos Fractured Aquifer (TFA). As the conjunctive use of stable isotopes and hydrogeochemical data provides additional information, we established a monitoring network for stable isotopes in precipitation in Cyprus. The local meteoric water line, altitude effect and seasonal variation of stable isotopes in precipitation are derived from monitoring data. Stable isotopes and hydrogeochemical data are combined to model water-rock interactions and groundwater evolution along a complete ophiolite sequence. As a result a generic hydrogeologic description for the observed water types is developed. Isotope hydrology was applied in conjunction with hydrogeochemical modelling in Kargiotis Watershed, a major north-south transect of the TFA. PHREEQC was used for hydrogeochemical modelling to establish generic descriptions for observed water types. Mean precipitation-weighted values from 16 monitoring stations were used to calculate the Local Meteoric Water Line (LMWL), which was found to be equal to δ2H = (6.58 ± 0.13)*δ18O + (12.64 ± 0.91). A general decrease of 1.22‰ for δ2H and 0.20‰ for δ18O in precipitation was calculated per 100 m altitude. A generic groundwater evolution path was established: 1. Na/MgClHCO3, 2. MgHCO3, 3. Ca/MgHCO3, 4. Ca/MgNaHCO3, 4a. MgNa/CaHCO3/Cl, 5. NaMg/CaHCO3/Cl, 6. NaHCO3, 7. Na/MgHCO3SO4, 8. NaSO4Cl/HCO3. Hydrogeologic descriptions, consisting of groundwater origin, flow path and possible active water-rock processes, have been realised for the observed water types. The first two water types occur in serpentine and ultramafic-gabbro springs. Type 3 waters represent early stages of recharge and/or short flow paths, in gabbro whereas types 4 and 5 are typical for further percolating waters in gabbro and diabase. Water types 6 and 7 occur both in diabase and in the basal group and represent the regional flow. Water type 8 is the end member of regional, upwelling groundwater in the basal group. The presented descriptions and methods have practical applications in groundwater exploration, characterization, and protection. The methodology can be applied in other complex aquifer systems.
Area: Cyprus
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Gardiner, J., Thomas, R. B., Phan, T. T., Stuckman, M., Wang, J., Small, M., et al. (2020). Utilization of produced water baseline as a groundwater monitoring tool at a CO2-EOR site in the Permian Basin, Texas, USA. Applied Geochemistry, 121, 104688.
Abstract: Carbon dioxide (CO2) enhanced oil recovery (EOR) provides a pathway for economic reuse and storage of CO2, a greenhouse gas. One challenge with this practice is ensuring CO2 injection does not result in target reservoir fluids migrating into overlying shallow (\textless1000 m) groundwater formations. Effective monitoring for leakage from storage formations could involve measuring sensitive chemical indicators in overlying groundwater units and within the producing formation itself for evidence of deviation from an initial state. In this study, produced waters and overlying groundwaters were monitored over a five-year period to evaluate which geochemical signals may be useful to ensure that oilfield produced waters did not impact overlying groundwaters. During this five-year period, a mature carbonate oil reservoir in the Permian Basin transitioned from a waterflooding operation to a water-alternating-gas injection (WAG), in which the formation was flooded with CO2 and various mixtures of produced water. Significant increases in dissolved inorganic constituents [alkalinity, TDS, Na+, Cl−, SO42−] were observed in produced waters following CO2 injection; however, carbonate reservoir dissolution-precipitation reactions appear to be minimal and injected CO2 appears to be stored via solubility trapping. Although there are statistically significant geochemical variations following CO2 injection, applying isometric log-ratios to certain parameters establishes a narrow range for post-CO2 injection produced waters. This narrow range can be considered a baseline for post-CO2 injection produced waters; this baseline can be utilized to monitor overlying local groundwaters for produced water intrusion. Additionally, certain parameters [Na+, Ca2+, K+, Cl−, alkalinity, and TDS] display large concentration disparities between produced water and overlying groundwaters; these parameters would be sensitive indicators of produced water intrusion into overlying groundwaters.
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Christofi, C., Bruggeman, A., Külls, C., & Constantinou, C. (2020). Hydrochemical evolution of groundwater in gabbro of the Troodos Fractured Aquifer. A comprehensive approach. Applied Geochemistry, 114, 104524.
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Ruiz, O., Thomson, B., Cerrato, J. M., & Rodriguez-Freire, L. (2019). Groundwater restoration following in-situ recovery (ISR) mining of uranium. Applied Geochemistry, 109, 104418.
Abstract: From 1950 through the early 1980’s New Mexico accounted for roughly half of domestic uranium (U) production for the nuclear power industry and the nation’s weapon programs. Increased interest in nuclear energy has led to proposals for renewed development using both underground mining and uranium in situ recovery (ISR). When feasible, ISR greatly reduces waste generated by the mining and milling processes, however, the ability to restore ground water to acceptable quality after ISR ends is uncertain. This research investigated two methods of stabilizing an aquifer following ISR. Batch and column studies were performed to evaluate chemical and biological methods of stabilization. Columns packed with ore were first leached with an aerated NaHCO3 ground water solution to simulate ISR. Constituents present at elevated concentrations after leaching included molybdenum (Mo), selenium (Se), U, and vanadium (V). Chemical stabilization was studied by passing a phosphate (PO43-) amended solution through the ore to achieve passivation of mineral surfaces by P precipitates. Microbial stabilization was studied by passing a lactate solution through the ore to stimulate growth of anaerobic metal- and sulfate-reducing organisms to reduce U and other elements to less soluble phases. Analyses of the solids from the columns after completion of these experiments by X-ray photo electron spectroscopy (XPS) identified phosphate on samples near the column inlet of the chemically stabilized columns. Microbial populations were characterized by Illumina DNA sequencing and confirmed the presence of metal- and sulfate-reducing organisms. Neither chemical nor microbial stabilization method achieved contaminant immobilization, which is believed due to limited mixing of the stabilization solutions with the contaminated leach solutions. These results emphasize that ground water hydrodynamics, especially mixing, must be considered in aquifer restoration of soluble constituents.
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Mühr-Ebert, E. L., Wagner, F., & Walther, C. (2019). Speciation of uranium: Compilation of a thermodynamic database and its experimental evaluation using different analytical techniques. Applied Geochemistry, 100, 213–222.
Abstract: Environmental hazards are caused by uranium mining legacies and enhanced radioactivity in utilized groundwater and surface water resources. Knowledge of uranium speciation in these waters is essential for predicting radionuclide migration and for installing effective water purification technology. The validity of the thermodynamic data for the environmental media affected by uranium mining legacies is of utmost importance. Therefore, a comprehensive and consistent database was established according to current knowledge. The uranium data included in the database is based on the NEA TDB (Guillaumont et al., 2003) and is modified or supplemented as necessary e.g. for calcium and magnesium uranyl carbonates. The specific ion interaction theory (Brönsted, 1922) is used to estimate activity constants, which is sufficient for the considered low ionic strengths. The success of this approach was evaluated by comparative experimental investigations and model calculations (PHREEQC (Parkhurst and Appelo, 1999)) for several model systems. The waters differ in pH (2.7–9.8), uranium concentration (10−9-10−4 mol/L) and ionic strength (0.002–0.2 mol/L). We used chemical extraction experiments, ESI-Orbitrap-MS and time-resolved laser-induced fluorescence spectroscopy (TRLFS) to measure the uranium speciation. The latter method is nonintrusive and therefore does not change the chemical composition of the investigated waters. This is very important, because any change of the system under study may also change the speciation.
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