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Hubbard, B.E.; Gallegos, T.J.; Stengel, V.; Hoefen, T.M.; Kokaly, R.F.; Elliott, B. |
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Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain |
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Journal Article |
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2024 |
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Journal of Geochemical Exploration |
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257 |
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107370 |
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Critical minerals, Hyperspectral, Industrial minerals, Mine waste, Texas coastal plain, Uranium |
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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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THL @ christoph.kuells @ hubbard_hyperspectral_2024 |
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178 |
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Grozeva, N.G.; Radwan, J.; Beaucaire, C.; Descostes, M. |
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Title |
Reactive transport modeling of U and Ra mobility in roll-front uranium deposits: Parameters influencing 226Ra/238U disequilibria |
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Journal Article |
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Year |
2022 |
Publication |
Journal of Geochemical Exploration |
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236 |
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106961 |
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Ra/U, Radioactive disequilibria, Radium, Reactive transport modeling, Roll-front uranium deposit |
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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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THL @ christoph.kuells @ grozeva_reactive_2022 |
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180 |
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Boulesteix, T.; Cathelineau, M.; Deloule, E.; Brouand, M.; Toubon, H.; Lach, P.; Fiet, N. |
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Ilmenites and their alteration products, sinkholes for uranium and radium in roll-front deposits after the example of South Tortkuduk (Kazakhstan) |
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Journal Article |
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2019 |
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Journal of Geochemical Exploration |
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206 |
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106343 |
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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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THL @ christoph.kuells @ boulesteix_ilmenites_2019 |
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181 |
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Hebert, B.; Baron, F.; Robin, V.; Lelievre, K.; Dacheux, N.; Szenknect, S.; Mesbah, A.; Pouradier, A.; Jikibayev, R.; Roy, R.; Beaufort, D. |
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Quantification of coffinite (USiO4) in roll-front uranium deposits using visible to near infrared (Vis-NIR) portable field spectroscopy |
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Journal Article |
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2019 |
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Journal of Geochemical Exploration |
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199 |
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53-59 |
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Coffinite, Mineral quantification, Near infrared, Ore exploration, Portable field spectroscopy, Roll-front deposits |
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Coffinite (USiO4) is a common uranium-bearing mineral of roll-front uranium deposits. This mineral can be identified by the visible near infrared (Vis-NIR) portable field spectrometers used in mining exploration. However, due to the low detection limits and associated errors, the quantification of coffinite abundance in the mineralized sandstones or sandy sediments of roll-front uranium deposits using Vis-NIR spectrometry requires a specific methodological development. In this study, the 1135 nm absorption band area is used to quantify the abundance of coffinite. This absorption feature does not interfere with NIR absorption bands of any other minerals present in natural sands or sandstones of uranium roll-front deposits. The correlation between the 1135 nm band area and coffinite content was determined from a series of spectra measured from prepared mineral mixtures. The samples were prepared with a range of weighted amounts of arenitic sands and synthetic coffinite simulating the range of uranium concentration encountered in roll-front uranium deposits. The methodology presented in this study provides the quantification of the coffinite content present in sands between 0.03 wt% to 1 wt% coffinite with a detection limit as low as 0.005 wt%. The integrated area of the 1135 nm band is positively correlated with the coffinite content of the sand in this range, showing that the method is efficient to quantify coffinite concentrations typical of roll-front uranium deposits. The regression equation defined in this study was then used as a reference to predict the amount of natural coffinite in a set of mineralized samples from the Tortkuduk uranium roll-front deposit (South Kazakhstan). |
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THL @ christoph.kuells @ hebert_quantification_2019 |
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184 |
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Bullock, L.A.; Parnell, J. |
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Selenium and molybdenum enrichment in uranium roll-front deposits of Wyoming and Colorado, USA |
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Journal Article |
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2017 |
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Journal of Geochemical Exploration |
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180 |
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101-112 |
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Molybdenum, Roll-fronts, Selenium, Tellurium, Uranium, Wyoming |
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Sandstone uranium (U) roll-front deposits of Wyoming and Colorado (USA) are important U resources, and may provide a terrestrial source for critical accessory elements, such as selenium (Se), molybdenum (Mo), and tellurium (Te). Due to their associated toxicity, MoSeTe occurrences in roll-fronts should also be carefully monitored during U leaching and ore processing. While elevated MoSe concentrations in roll-fronts are well established, very little is known about Te occurrence in such deposits. This study aims to establish MoSeTe concentrations in Wyoming and Colorado roll-fronts, and assess the significance of these deposits in an environmental and mineral exploration context. Sampled roll-front deposits, produced by oxidized groundwater transportation through a sandstone, show high MoSe content in specific redox zones, and low Te, relative to crustal means. High Se concentrations (up to 168ppm) are restricted to a narrow band of alteration at the redox front. High Mo content (up to 115ppm) is typically associated with the reduced mineralized nose and seepage zones of the roll-front, ahead of the U orebody. Elevated trace element concentrations are likely sourced from proximal granitic intrusions, tuffaceous deposits, and local pyritic mudstones. Elevated MoSe content in the sampled roll fronts may be regarded as a contaminant in U in-situ recovery and leaching processing, and may pose an environmental threat in groundwaters and soils, so extraction should be carefully monitored. The identification of peak concentrations of MoSe can also act as a pathfinder for the redox front of a roll-front, and help to isolate the U orebody, particularly in the absence of gamma signatures. |
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THL @ christoph.kuells @ bullock_selenium_2017 |
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189 |
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Rubin, R. |
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Water conservation methods in Israel’s Negev desert in late antiquity |
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1988 |
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Journal of Historical Geography |
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14 |
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3 |
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229-244 |
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Settlement in Israel’s Negev desert historically has been dependent on water conservation techniques. Fieldwork carried out on settlement sites constructed during the Byzantine period, when agriculture and trade flourished, revealed a variety of water installations some of which are in use today. Perennial springs in the Negev are generally small and difficult of access. Cisterns were the most common conservation devices and came in both large, enclosed and single, open forms. Cisterns were common particularly in the towns, where they were usually built as part of house foundations. Dams were discovered at several sites but proved to be inefficient and easily abandoned because of evaporation and siltation problems. Public reservoirs were part of the structure of the largest towns and were open and among the larges structures uncovered at settlement sites. Wells were distributed widely throughout the desert and were part of the only conservation system that did not depend directly on surface rainfall. A qanat system was located in the eastern Negev dating from the late settlement period before the area was abandoned at the turn of the eighth century. These various water systems raise questions about their builders and their origins, and suggests that builders originating in more humid Mediterranean environments tended to produce less adaptable installations than builders derived from the south or the east. |
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0305-7488 |
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THL @ christoph.kuells @ Rubin1988229 |
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262 |
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Rooyen, J.D. van; Watson, A.W.; Miller, J.A. |
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Using tritium and radiocarbon activities to constrain regional modern and fossil groundwater mixing in Southern Africa |
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2022 |
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Journal of Hydrology |
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614 |
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128570 |
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Radiocarbon, Residence time, SADC, Tritium |
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This study combines historical records of 14C and 3H in the atmosphere and soil with renewal rate and groundwater lumped parameter models to predict the abundance of 14C and 3H in groundwater over time. 624 groundwater samples from numerous studies, over four decades (1978–2019), in South Africa, Namibia, Botswana and Mozambique were collated to compare with predicted groundwater activities of 14C and 3H within the South African Development Community (SADC) region. Spatial datasets of carbonate bearing lithology, C3/C4 vegetation, summer/winter rainfall and coastal proximity were used to apply corrections to 14C and 3H data. Corrected values of 14C and 3H were compared with the theoretical abundance of these tracers, derived from the lumped parameter models, to estimate the general mean residence times and presence of groundwater mixing between modern recharge and older groundwaters. This study found that corrected values produced varying mean residence times derived from 14C ages (∼500–28500 years) and a wide range of potentially mixed waters within each aquifer system (0–100 % of tested wells) across the study area. The largest proportions of mixed groundwater, as well as the youngest mean residence times, were found in alluvial and primary fractured rock aquifers (e.g., western coast of South Africa and southern Mozambique). The smallest proportions of mixed groundwater were predicted in deep confined clay-rich aquifers as well as layered coal bearing carbonate sequences (e.g., Orapa, Malwewe and Serowe, Botswana). Insights into the proportions of mixed groundwater and mean residence times can help assess hydrological resilience on a regional scale. Such information is pertinent in promoting socio-economic development and increased water/food security in the SADC region. By understanding the resilience of groundwater resources, robust and informed strategies for water equality and GDP growth in the SADC region can be envisioned and implemented. |
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0022-1694 |
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THL @ christoph.kuells @ rooyen_using_2022 |
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94 |
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Heaton, T.H.E.; Talma, A.S.; Vogel, J.C. |
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Origin and history of nitrate in confined groundwater in the western Kalahari |
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1983 |
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Journal of Hydrology |
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62 |
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1 |
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243-262 |
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Data are presented for nitrate, dinitrogen and argon concentrations and 15N14N ratios in groundwater, with radiocarbon ages up to 40,000 yr. for three confined sandstone aquifers in the western Kalahari of South West Africa/Namibia. The nitrate is probably generated within the soil of the recharge areas, and its production rate during the period 3000-40,000 B.P. has remained between 0.5 and 1.6 meq NO−3l−1 of recharge water, with ° 15N between + 4 and + 8‰. Variations in the amount of nitrate and of “excess air” in groundwater recharge are found, and can only reflect changes in the environmental conditions during recharge. They must therefore be caused by the climatic changes that have taken place during the past 25,000 yr. |
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0022-1694 |
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THL @ christoph.kuells @ heaton_origin_1983 |
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95 |
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Frumkin, A.; Gvirtzman, H. |
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Cross-formational rising groundwater at an artesian karstic basin: the Ayalon Saline Anomaly, Israel |
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Journal Article |
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2006 |
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Journal of Hydrology |
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318 |
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1 |
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316-333 |
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Confined karst, Groundwater, HS, Maze caves, Rising water, Yarkon–Taninim aquifer |
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It is proposed that a geothermal artesian karstic system at the central part of the Yarkon–Taninim aquifer creates the ‘Ayalon Saline Anomaly’ (ASA), whose mechanism has been under debate for several decades. A 4-year-long detailed groundwater monitoring was carried out at 68 new shallow boreholes in the Ayalon region, accompanied by a comprehensive survey of karstic voids. Results indicate the rising of warm-brackish groundwater through highly permeable swarms of karstic shafts, serving as an outflow of the artesian geothermal system. The ASA area contains ‘hot spots’, where groundwater contrasts with ‘normal’ water hundreds of meters away. The ASA temperature reaches 30°C (∼5°C warmer than its surroundings), chloride concentration reaches 528mg/l (50–100mg/l in the surrounding), H2S concentration reaches 5.6mg/l (zero all around) and pH value is 7.0 (compared with 7.8 around). Subsequently, the hydrothermal water flows laterally of at the watertable horizon through horizontal conduits, mixing with ‘normal’ fresh water which had circulated at shallow depth. Following rainy seasons, maximal watertable rise is observed in the ASA compared to its surroundings. Regional hydrogeology considerations suggest that the replenishment area for the ASA water is at the Samaria Mountains, east of the ASA. The water circulates to a great depth while flowing westward, and a cross-formational upward flow is then favored close the upper sub-aquifer’s confinement border. |
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0022-1694 |
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THL @ christoph.kuells @ frumkin_cross-formational_2006 |
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117 |
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Gimeno, M.J.; Tullborg, E.-L.; Nilsson, A.-C.; Auqué, L.F.; Nilsson, L. |
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Hydrogeochemical characterisation of the groundwater in the crystalline basement of Forsmark, the selected area for the geological nuclear repositories in Sweden |
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2023 |
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Journal of Hydrology |
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624 |
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129818 |
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Crystalline bedrock, Deep geological repository, Glacial meltwater intrusion, Groundwater mixing, Hydrogeochemical model, Nuclear waste disposal |
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Abstract |
Numerous groundwater analyses from the crystalline bedrock in the Forsmark area have been performed between 2002 and 2019, together with thorough geological, geophysical, and hydrogeological studies, within the site investigations carried out by the Swedish Nuclear Fuel and Waste Management Company. The groundwater samples have been taken from boreholes down to ≈ 1000 m and the analysis include major- and trace-elements, stable and radiogenic isotopes, gases and microbes. The chemical and isotopic composition of these groundwaters evidences the presence of non-marine brackish to saline groundwaters with very long residence times (many hundreds of thousands of years) and a series of complex mixing events resulting from the recharge of different waters over time: glacial meltwaters, probably from different glaciations of which the latest culminated some 20,000 years ago, and marine waters from the Baltic starting some 7000 years ago. Later, meteoric water and present Baltic Sea water have recharged in different parts of the upper 100 m. These mixing events have also triggered chemical and microbial reactions that have conditioned some of the important groundwater parameters and, together with the structural complexity of the area, they have promoted a heterogeneous distribution of groundwater compositions in the bedrock. Due to these evident differences in chemistry, residence time and origin of the groundwater, several groundwater types were defined in order to facilitate the visualisation and communication. The differentiation (linked to the paleohydrological history of the area) was based on Cl concentration, Cl/Mg ratio (marine component), and δ18O value (glacial component). The work presented in this paper increases the understanding of the groundwater evolution in fractured and compartmentalised aquifers where mixing processes are the most important mechanisms. The model proposed to characterise the present groundwater system of the Forsmark area will also help to predict the future hydrogeochemical behaviour of the groundwater system after the construction of the repositories for the nuclear wastes. |
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0022-1694 |
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THL @ christoph.kuells @ gimeno_hydrogeochemical_2023 |
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137 |
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