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Author Ruiz, O.; Thomson, B.; Cerrato, J.M.; Rodriguez-Freire, L. url  openurl
  Title Groundwater restoration following in-situ recovery (ISR) mining of uranium Type Journal Article
  Year 2019 Publication Applied Geochemistry Abbreviated Journal  
  Volume 109 Issue Pages 104418  
  Keywords Aquifer stabilization, Ground water restoration, In-situ leach mining, In-situ recovery, Uranium  
  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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  Call Number THL @ christoph.kuells @ ruiz_groundwater_2019 Serial 153  
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Author Gardiner, J.; Thomas, R.B.; Phan, T.T.; Stuckman, M.; Wang, J.; Small, M.; Lopano, C.; Hakala, J.A. url  openurl
  Title Utilization of produced water baseline as a groundwater monitoring tool at a CO2-EOR site in the Permian Basin, Texas, USA Type Journal Article
  Year 2020 Publication Applied Geochemistry Abbreviated Journal  
  Volume 121 Issue Pages 104688  
  Keywords CO storage, Enhanced oil recovery, Geochemical baseline, Groundwater monitoring, Produced water, Solubility trapping  
  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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  Call Number THL @ christoph.kuells @ gardiner_utilization_2020 Serial 171  
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Author Lima, G.F.C.; Filho, C.A. de C.; Ferreira, V.G.; Lima, J. da S.D.; Marques, E.D.; Minardi, P.S.P.; Dalmázio, I.; Moreira, R.M. url  openurl
  Title 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 Type Journal Article
  Year 2023 Publication Applied Geochemistry Abbreviated Journal  
  Volume 159 Issue Pages 105818  
  Keywords Fracking, Groundwater dating, Indaiá river, Isotopes assessment, Shale gas, Unconventional hydrocarbons  
  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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  Call Number THL @ christoph.kuells @ lima_establishing_2023 Serial 173  
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Author Qiu, W.; Yang, Y.; Song, J.; Que, W.; Liu, Z.; Weng, H.; Wu, J.; Wu, J. url  openurl
  Title 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 Type Journal Article
  Year 2023 Publication Applied Geochemistry Abbreviated Journal  
  Volume 148 Issue Pages 105522  
  Keywords Carbonate minerals, In-situ leaching (ISL) of uranium, Pyrite oxidation, Reactive transport modeling (RTM)  
  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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  Call Number THL @ christoph.kuells @ qiu_what_2023 Serial 207  
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Author Heine, F.; Einsiedl, F. url  openurl
  Title Groundwater dating with dissolved organic radiocarbon: A promising approach in carbonate aquifers Type Journal Article
  Year 2021 Publication Applied Geochemistry Abbreviated Journal  
  Volume 125 Issue Pages 104827  
  Keywords C groundwater dating, deep carbonate aquifer, DOC, SPE-PPL  
  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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  Call Number THL @ christoph.kuells @ Heine2021104827 Serial 216  
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Author Wilson, G.B.; McNeill, G.W. url  openurl
  Title Noble gas recharge temperatures and the excess air component Type Journal Article
  Year 1997 Publication Applied Geochemistry Abbreviated Journal  
  Volume 12 Issue 6 Pages 747-762  
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  Abstract The calculation of a groundwater recharge temperature based on the dissolved concentrations of Ne, Ar, Kr and Xe requires a correction for noble gas supersaturation due to excess air entrainment. This entrainment is commonly attributed to the recharge process or to air contamination at the wellhead during sample collection. With the exception of some local studies, most work has concentrated on interpretation of the recharge temperature or quantification of the radiogenic content for palaeoclimatic and dating purposes. The magnitude and source of the excess air is not directly relevant to these studies and so is often ignored. In this work, excess air Ne and other data have been calculated from new and published noble gas data sets for several groundwater systems. For younger groundwaters which have been recharged under one broad climatic regime, the amount of air entrainment increases according to lithology in the order granites, sandstones and limestones respectively. A negative correlation between precipitation and excess air entrainment is identified in at least one aquifer, and some of the mechanisms which may influence the entrainment process are discussed.  
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  Call Number THL @ christoph.kuells @ Wilson1997747 Serial 281  
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Author Vogel, J.C.; Talma, A.S.; Heaton, T.H.E.; Kronfeld, J. url  openurl
  Title Evaluating the rate of migration of an uranium deposition front within the Uitenhage Aquifer Type Journal Article
  Year 1999 Publication Journal of Geochemical Exploration Abbreviated Journal  
  Volume 66 Issue 1 Pages 269-276  
  Keywords redox changes in aquifer, sandstone-type uranium deposit, South Africa, uranium series  
  Abstract The solubility of uranium in groundwater is very sensitive to changes in redox conditions. Many secondary (sandstone-type) uranium deposits have been formed when soluble U has precipitated after encountering reducing conditions in the subsurface. In the groundwater of the Uitenhage Aquifer (Cape Province, South Africa), 238U-series isotopes were used to assist in studying the history of the reducing barrier. Uranium isotopes were used to determine the present position of the barrier. Radium and radon were used to evaluate the path of migration that the front of the oxygen depletion zone has taken over the past 105 years. During this time the reducing barrier has moved, leaving in its wake a trail of U in various stages of secular equilibrium with its daughter 230Th. The 226Ra daughter of 230Th is not very mobile. Its growth upon the aquifer wall is reflected in the Rn content of the water. This in turn, due to the relatively great age of the water, indicates the extent of the 230Th ingrowth (from precipitated U) that took place before the barrier migrated.  
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  Call Number THL @ christoph.kuells @ vogel_evaluating_1999 Serial 126  
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Author Hubbard, B.E.; Gallegos, T.J.; Stengel, V.; Hoefen, T.M.; Kokaly, R.F.; Elliott, B. url  openurl
  Title Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain Type Journal Article
  Year 2024 Publication Journal of Geochemical Exploration Abbreviated Journal  
  Volume 257 Issue Pages 107370  
  Keywords Critical minerals, Hyperspectral, Industrial minerals, Mine waste, Texas coastal plain, Uranium  
  Abstract VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey’s (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA. Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite. Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data. The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.  
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  Call Number THL @ christoph.kuells @ hubbard_hyperspectral_2024 Serial 178  
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Author Grozeva, N.G.; Radwan, J.; Beaucaire, C.; Descostes, M. url  openurl
  Title Reactive transport modeling of U and Ra mobility in roll-front uranium deposits: Parameters influencing 226Ra/238U disequilibria Type Journal Article
  Year 2022 Publication Journal of Geochemical Exploration Abbreviated Journal  
  Volume 236 Issue Pages 106961  
  Keywords Ra/U, Radioactive disequilibria, Radium, Reactive transport modeling, Roll-front uranium deposit  
  Abstract Uranium reserve estimates in ore deposits can be significantly impacted by 226Ra/238U disequilibria arising from the differential mobility of uranium and radium during groundwater transport. 1D reactive transport models were developed to investigate the long-term effects of retention processes (UO2(am) precipitation, U(VI) and Ra sorption on smectite, Ra co-precipitation with barite) on the repartitioning of 238U and 226Ra during formation of roll-front type deposits. Analytical solutions to radioactive decay chains were used in complement to examine the influence of geochemical parameters, including fluid 234U/238U activity ratios and α-recoil loss, on 226Ra/238U disequilibria in uranium ores. Model results demonstrate that smectite and barite can produce 226Ra/238U ratios \textgreater1 at low uranium contents and may explain 226Ra/238U disequilibria occurring in altered rock up- and downstream of roll-front deposits. The capacity of these phases to take up Ra and generate 226Ra/238U disequilibria depends on both mineral contents and groundwater compositions, and is thus expected to be site-specific. Simulations of ore deposits that advance downstream with time demonstrate the formation of stronger 226Ra/238U disequilibria, as expected, in the downgradient side or nose of the ore, reflecting both younger mineralization ages and the presence of active uranium precipitation. Whether disequilibria are positive or negative with respect to secular equilibrium, however, depends on the 234U/238U activity ratio in the fluid from which uranium minerals precipitate. Smaller hydraulic conductivities are shown to generate a narrower range in 226Ra/238U activity ratios with distance, and may explain the occurrence of disequilibria in the limb ore that are less pronounced than those in the nose. Furthermore, the ability of α-recoil loss to decrease 226Ra/238U activity ratios at secular equilibrium may account for negative disequilibria in high grade ores. The South Tortkuduk uranium deposits (Kazakhstan) are subsequently used as a case study to identify the processes and parameters that may contribute to 226Ra/238U disequilibria at this site. Variations in multiple parameters, including clay contents, barite contents, and mineralization ages, are found to reproduce measured 226Ra/238U activity ratios in the roll-front ore. Prioritization of these parameters will necessitate field measurements targeting both groundwater fluids and the host rock. Results from this study will ultimately aid geologists in building appropriate hydrogeochemical data sets to more efficiently locate and exploit uranium ore deposits.  
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  Call Number THL @ christoph.kuells @ grozeva_reactive_2022 Serial 180  
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Author Boulesteix, T.; Cathelineau, M.; Deloule, E.; Brouand, M.; Toubon, H.; Lach, P.; Fiet, N. url  openurl
  Title Ilmenites and their alteration products, sinkholes for uranium and radium in roll-front deposits after the example of South Tortkuduk (Kazakhstan) Type Journal Article
  Year 2019 Publication Journal of Geochemical Exploration Abbreviated Journal  
  Volume 206 Issue Pages 106343  
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  Abstract The approximate determination of average Ra/U disequilibria in orebodies is one of the most common causes of errors in U reserve estimations. In roll-front deposits, the disequilibria are however frequently distributed following complex geometries, which must be fully understood to prevent major U reserve overestimates and costly unproductive extractive operations. The processes responsible for disruption of the radioactive equilibria and the U and Ra carriers in such complex natural systems remain poorly constrained. In this contribution, we propose an innovative approach, mixing orebody to sub-grain scale studies to unravel the distribution of U and Ra and the processes responsible for their concentration and uncoupling. Using mineral separations, gamma spectrometry and mineral-chemical analyses, we identified the Fe-Ti clusters (altered ilmenite + pyrite/marcasite) as the microsites for coffinite precipitation and Ra concentration. To understand the influence of such clusters on the distribution of U and Ra at the deposit scale, whole-rock Ra/U disequilibria were measured and mapped at a series of ten drill holes along a profile crosscutting the studied roll-front. The main Ra/U disequilibria are encountered around the mineralization in low U content zones. They are controlled by two main processes. (1) In the oxidized zones, the immobility of 230Th with respect to the U produces patches of Ra disequilibria (carried by the altered U minerals). (2) In the immediate vicinity of the roll-front, the dissolution of the mineralization produces an Ra flux trapped by the alteration products of ilmenites, as definitely confirmed by direct SIMS measurements. Such a process is responsible for the Ra disequilibria envelope located downstream of the richest ores, also known as Ra halo. The highest Ra/U ratios correspond to oxidized upstream samples, but most other high Ra/U ratios are from reduced downstream samples close to the mineralization. Such a low to medium U content envelope with high Ra/U ratios constitutes the main cause of U reserve overestimations.  
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  Call Number THL @ christoph.kuells @ boulesteix_ilmenites_2019 Serial 181  
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