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Etschmann, B.; Liu, W.; Li, K.; Dai, S.; Reith, F.; Falconer, D.; Kerr, G.; Paterson, D.; Howard, D.; Kappen, P.; Wykes, J.; Brugger, J. |
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Title |
Enrichment of germanium and associated arsenic and tungsten in coal and roll-front uranium deposits |
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Journal Article |
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2017 |
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Chemical Geology |
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463 |
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29-49 |
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Arsenic, Coal, EXAFS and XANES, germanium, Hydrothermal fluids, Metallogenesis, Speciation, Tungsten |
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Most of the World’s germanium (Ge) is mined from Ge-rich lignite, where it is commonly associated with elevated arsenic (As), tungsten (W) and beryllium (Be) contents. Over the past decade, new evidence showing that World-class Ge deposits result from the interaction of hydrothermal fluids with organic matter in coal seams has emerged. Yet, the chemical state of Ge and associated metals in lignite remains poorly understood. We used Mega-pixel Synchrotron X-ray Fluorescence (MSXRF), X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) to characterize the oxidation states and chemical bonding environment of Ge, As, and W in two world-class Mesozoic Ge-in-lignite deposits (Lincang, Yunnan, southwestern China; Wulantuga, Inner Mongolia, northeastern China); in lignite-bearing uranium (U) ores from the Beverley deposit (South Australia) hosted in Eocene sandstones; and in lignite and preserved wood in late Oligocene-Miocene fluviatile sediments (Gore, Southland, New Zealand). The aim was to improve our understanding of the enrichment mechanism of Ge in lignite and better evaluate the environmental mobility of Ge and some of the associated metals (specifically As and W) in lignite ores. In all samples, chemical maps show that Ge is distributed homogeneously (down to 2μm) within the organic matter. XANES and EXAFS data show that Ge exists in the tetravalent oxidation state and in a distorted octahedral coordination with O, consistent with complexing of Ge by organic ligands. In some pyrite-bearing samples, a minor fraction of Ge is also present as Ge(IV) in association with pyrite. In contrast, As displays a more complex speciation pattern, sometimes even in a single sample, including As(III), As(V), and As(−I/+II) in solid solution in sulfides. Arsenic in sulfides occurs in anionic and cationic forms, i.e., it shows both the common substitution for S22− and the substitution for Fe recently discovered in some hydrothermal pyrites. Tungsten was present as W(VI) in distorted octahedral (3+3) coordination. The EXAFS data confirm the absence or minor contribution of individual W-rich minerals such as scheelite or ferberite to W mass balance in the studied samples. These data show that Ge, W, and probably some As are scavenged via formation of insoluble, oxygen-bridged metal organic complexes in lignite. Destruction of the organic ligands responsible for fixing Ge and W (As) in these lignites is required for liberating the metals, e.g. from waste materials. Geochemical modelling suggests that Ge, W, Be and As all can be extracted from granitic rocks by dilute, low temperature hydrothermal fluids. Germanium is transported mainly as the tetrahedral Ge(OH)4(aq) complex, but fixed as an octahedral oxy-bridged organic complex. The same situation is valid for W, which is transported at the tetrahedral tungstate ion, but most likely scavenged via formation of a 6-coordinated metal-organic species. The Ge-Be-W±As association in Ge-rich coals reflects the source of the metals as well as related scavenging mechanisms. |
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0009-2541 |
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THL @ christoph.kuells @ etschmann_enrichment_2017 |
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183 |
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Ammar, F.H.; Deschamps, P.; Chkir, N.; Zouari, K.; Agoune, A.; Hamelin, B. |
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Title |
Uranium isotopes as tracers of groundwater evolution in the Complexe Terminal aquifer of southern Tunisia |
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Journal Article |
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Year |
2020 |
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Quaternary International |
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547 |
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33-49 |
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CT southern Tunisia, Holocene, Mixing, Radicarbon, Uranium isotopes, Water-rock interaction |
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The Complexe Terminal (CT) multi-layer aquifer is formed by Neogene/Paleogene sand deposits, Upper Senonian (Campanian-Maastrichtian limestones) and Turonian carbonates. The chemical composition and isotopes of carbon and uranium were investigated in groundwater sampled from the main hydrogeological units of the (CT) aquifer in southern Tunisia. We paid special attention to the variability of uranium contents and isotopes ratio (234U/238U) to provide a better understanding of the evolution of the groundwater system. Uranium concentrations range from 1.5 to 19.5 ppb, typical of oxic or mildly reducing conditions in groundwaters. The lowest concentrations are found southeast of the study area, where active recharge is supposed to take place. When looking at the isotope composition, it appears that all the samples, including those from carbonate levels, are in radioactive disequilibrium with significant 234U excess. A clear-cut distinction is observed between Turonian and Senonian carbonate aquifers on the one hand, with 234U/238U activity ratios between 1.1 and 1.8, and the sandy aquifer on the other hand, showing higher ratios from 1.8 to 3.2. The distribution of uranium in this complex aquifer system seems to be in agreement with the lithological variability and are ultimately a function of a number of physical and chemical factors including the uranium content of the hosting geological formation, water-rock interaction and mixing between waters having different isotopic signatures. Significant relationships also appear when comparing the uranium distribution with the major ions composition. It is noticeable that uranium is better correlated with sulfate, calcium and magnesium than with other major ions as chloride or bicarbonate. The 14C activities and δ13C values of DIC cover a wide range of values, from 1.1 pmc to 30.2 pmc and from −3.6‰ to −10.7‰, respectively. 14C model ages estimated by the Fontes and Garnier model are all younger than 22 Ka and indicate that the recharge of CT groundwater occurred mainly during the end of the last Glacial and throughout the Holocene. |
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1040-6182 |
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THL @ christoph.kuells @ ammar_uranium_2020 |
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119 |
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Stone, A.E.C.; Thomas, D.S.G. |
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Casting new light on late Quaternary environmental and palaeohydrological change in the Namib Desert: A review of the application of optically stimulated luminescence in the region |
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Journal Article |
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2013 |
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Journal of Arid Environments |
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93 |
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40-58 |
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Namib Desert, Optically stimulated luminescence dating, Palaeoenvironment, Palaeohydrology, Quaternary, Southern Africa |
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The application of optically stimulated luminescence (OSL) dating in the Namib Desert is casting new light on late Quaternary environments. OSL has been applied to: (i) complex linear dunes, alongside ground penetrating radar stratigraphy in order to establish dune migration rates, (ii) fluvial lithofacies associations that distinguish between flood deposits and river end points, in order to constrain the timing of periods of higher discharge and conditions relatively drier than present and (iii) aeolian sand interbedded with carbonate deposits in order to provide chronologies for water-lain interdune sediments. We present and review the contribution of these data to enhancing reconstructions of the palaeoenvironments and palaeohydrology of the west coast of Namibia, particularly the increased confidence in interpretations provided by lithofacies analysis of the river deposits. This includes major silt deposits, which have had a contested palaeohydrological interpretation, such as the Kuiseb River Homeb Silts. We conclude that OSL should remain a key chronological technique to further elucidate the palaeoenvironmental history of southern Africa. |
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0140-1963 |
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THL @ christoph.kuells @ stone_casting_2013 |
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98 |
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Stone, A.E.C.; Edmunds, W.M. |
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Title |
Naturally-high nitrate in unsaturated zone sand dunes above the Stampriet Basin, Namibia |
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Journal Article |
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2014 |
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Journal of Arid Environments |
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105 |
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41-51 |
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Kalahari, Namibia, Nitrate in the unsaturated zone, Stampriet Basin, Transboundary basin, Unsaturated zone recharge |
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Elevated groundwater nitrate levels are common in drylands, often in excess of WHO guidelines, with concern for human and animal health. In light of recent attempts to identify nitrate sources in the Kalahari this paper presents the first unsaturated zone (USZ) nitrate profiles and recharge rate estimates for the important transboundary Stampriet Basin, alongside the first rainfall chemistry records. Elevated subsurface nitrate reaches 100–250 and 250–525 mg/L NO3–N, with NO3–N/Cl of 4–12, indicating input above evapotranspiration. Chloride mass balance recharge rates range from 4 to 27 mm/y, indicating a vertical movement of these nitrate pulses toward the water table over multi-decadal timescales. These profiles are sampled from dune crests, away from high concentrations of animals and without termite mounds. Given low-density animal grazing is unlikely to contribute consistent spot-scale nitrate over decades, these profiles give an initial estimate of naturally-produced concentrations. This insight is important for the management of the Stampriet Basin and wider Kalahari groundwater. This study expands our knowledge about elevated nitrate in dryland USZs, demonstrating that it can occur as pulses, probably in response to transient vegetation cover and that it is not limited to long-residence time USZs with very limited downward moisture flux (recharge). |
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0140-1963 |
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THL @ christoph.kuells @ stone_naturally-high_2014 |
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91 |
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Stone, A.E.C.; Edmunds, W.M. |
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Naturally-high nitrate in unsaturated zone sand dunes above the Stampriet Basin, Namibia |
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Journal Article |
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2014 |
Publication |
Journal of Arid Environments |
Abbreviated Journal |
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105 |
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41-51 |
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Kalahari, Namibia, Nitrate in the unsaturated zone, Stampriet Basin, Transboundary basin, Unsaturated zone recharge |
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Elevated groundwater nitrate levels are common in drylands, often in excess of WHO guidelines, with concern for human and animal health. In light of recent attempts to identify nitrate sources in the Kalahari this paper presents the first unsaturated zone (USZ) nitrate profiles and recharge rate estimates for the important transboundary Stampriet Basin, alongside the first rainfall chemistry records. Elevated subsurface nitrate reaches 100–250 and 250–525 mg/L NO3–N, with NO3–N/Cl of 4–12, indicating input above evapotranspiration. Chloride mass balance recharge rates range from 4 to 27 mm/y, indicating a vertical movement of these nitrate pulses toward the water table over multi-decadal timescales. These profiles are sampled from dune crests, away from high concentrations of animals and without termite mounds. Given low-density animal grazing is unlikely to contribute consistent spot-scale nitrate over decades, these profiles give an initial estimate of naturally-produced concentrations. This insight is important for the management of the Stampriet Basin and wider Kalahari groundwater. This study expands our knowledge about elevated nitrate in dryland USZs, demonstrating that it can occur as pulses, probably in response to transient vegetation cover and that it is not limited to long-residence time USZs with very limited downward moisture flux (recharge). |
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0140-1963 |
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THL @ christoph.kuells @ Stone201441 |
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218 |
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Author |
Stone, A.E.C.; Edmunds, W.M. |
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Title |
Naturally-high nitrate in unsaturated zone sand dunes above the Stampriet Basin, Namibia |
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Journal Article |
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Year |
2014 |
Publication |
Journal of Arid Environments |
Abbreviated Journal |
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105 |
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41-51 |
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Keywords |
Kalahari, Namibia, Nitrate in the unsaturated zone, Stampriet Basin, Transboundary basin, Unsaturated zone recharge |
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Abstract |
Elevated groundwater nitrate levels are common in drylands, often in excess of WHO guidelines, with concern for human and animal health. In light of recent attempts to identify nitrate sources in the Kalahari this paper presents the first unsaturated zone (USZ) nitrate profiles and recharge rate estimates for the important transboundary Stampriet Basin, alongside the first rainfall chemistry records. Elevated subsurface nitrate reaches 100–250 and 250–525 mg/L NO3–N, with NO3–N/Cl of 4–12, indicating input above evapotranspiration. Chloride mass balance recharge rates range from 4 to 27 mm/y, indicating a vertical movement of these nitrate pulses toward the water table over multi-decadal timescales. These profiles are sampled from dune crests, away from high concentrations of animals and without termite mounds. Given low-density animal grazing is unlikely to contribute consistent spot-scale nitrate over decades, these profiles give an initial estimate of naturally-produced concentrations. This insight is important for the management of the Stampriet Basin and wider Kalahari groundwater. This study expands our knowledge about elevated nitrate in dryland USZs, demonstrating that it can occur as pulses, probably in response to transient vegetation cover and that it is not limited to long-residence time USZs with very limited downward moisture flux (recharge). |
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0140-1963 |
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THL @ christoph.kuells @ Stone201441 |
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279 |
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Severi, A.; Masoudian, M.; Kordi, E.; Roettcher, K. |
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Discharge coefficient of combined-free over-under flow on a cylindrical weir-gate |
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2015 |
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ISH Journal of Hydraulic Engineering |
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21 |
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1 |
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42-52 |
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Taylor & Francis |
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THL @ christoph.kuells @ doi:10.1080/09715010.2014.939503 |
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88 |
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Merembayev, T.; Yunussov, R.; Yedilkhan, A. |
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Machine Learning Algorithms for Stratigraphy Classification on Uranium Deposits |
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Journal Article |
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2019 |
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Procedia Computer Science |
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150 |
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46-52 |
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classification, geophysics logging data, machine learning, stratigraphy, uranium deposit |
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Machine learning today becomes more and more effective instrument to solve many particular problems, where there are difficulties to apply well known and described math model. In other words – it is a great tool to describe non-linear phenomena. We tried to use this technique to improve existing process of stratigraphy, and reduce costs on site by applying computer leaded predictions on the basis of existing on-field collected data. Article describes usage of machine learning algorithms for stratigraphy boundaries classification based on geophysics logging data for uranium deposit in Kazakhstan. Correct marking of stratigraphy from geophysics logging data is complex non-linear task. To solve this task we applied several algorithms of machine learning: random forest, logistic regression, gradient boosting, k nearest neighbour and XGBoost. |
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1877-0509 |
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THL @ christoph.kuells @ merembayev_machine_2019 |
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113 |
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Khoury, H.N.; salameh, E.M.; Clark, I.D. |
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Mineralogy and origin of surficial uranium deposits hosted in travertine and calcrete from central Jordan |
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Journal Article |
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2014 |
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Applied Geochemistry |
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43 |
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49-65 |
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Secondary uranium encrustations are hosted in thick travertine and calcrete deposits of Pleistocene–Recent age in central Jordan. The central Jordan varicolored marble and travertine are equivalent to the active metamorphic area in Maqarin, north Jordan. More than 100 samples were collected from the outcrops of the varicolored marble, travertine, calcrete, and the yellow uranium encrustations. The secondary yellow encrustations are mainly composed of uranyl vanadate complexes. Tyuyamunite Ca(UO2)2V25+O8·3(H2O)–strelkinite Na2(UO2)2V2O8·6(H2O) solid solution series are the major components and their composition reflects changes in the Ca/Na ratio in solution. Potentially, new vanadium free calcium uranate phases (restricted to the varicolored marble) were identified with CaO:UO3 ratios different from the known mineral vorlanite (CaU6+)O4. Carbon and oxygen isotope data from calcite in the varicolored marble are characterized by Rayleigh-type enrichment in light isotopes associated with release of 13C and 18O enriched CO2 by high temperature decarbonation during combustion of the bituminous marl. Stable isotope results from uranium hosted travertine and calcrete varieties exhibit a wide range in isotopic values, between decarbonated and normal sedimentary carbonate rocks. The depleted δ13C and δ18O values in the travertine are related to the kinetic reaction of atmospheric CO2 with hyperalkaline Ca(OH)2 water. The gradual enrichment of δ13C and δ18O values in the calcrete towards equilibrium with the surrounding environment is related to continuous evaporation during seasonal dry periods. Uranium mineralization in central Jordan resulted from the interplay of tectonic, climatic, hydrologic, and depositional events. The large distribution of surficial uranium occurrences hosted in travertine and calcrete deposits is related to the artesian ascending groundwater that formed extensive lakes along NNW–SSE trending depressions. Fresh groundwater moved upward through the highly fractured phosphate, bituminous marl and varicolored marble to form unusual highly alkaline water (hydroxide–sulfate type) enriched with sensitive redox elements among which were U and V. |
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0883-2927 |
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THL @ christoph.kuells @ khoury_mineralogy_2014 |
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121 |
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Hall, S.M.; Gosen, B.S.V.; Paces, J.B.; Zielinski, R.A.; Breit, G.N. |
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Calcrete uranium deposits in the Southern High Plains, USA |
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Journal Article |
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2019 |
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Ore Geology Reviews |
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109 |
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50-78 |
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Calcrete, Carnotite, Finchite, Geochemistry, Uranium, Vanadium |
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The Southern High Plains (SHP) is a new and emerging U.S. uranium province. Here, uranyl vanadates form deposits in Pliocene to Pleistocene sandstone, dolomite, and limestone. Fifteen calcrete uranium occurrences are identified; two of these, the Buzzard Draw and Sulfur Springs Draw deposits, have combined in-place resources estimated at about 4 million pounds of U3O8. Ore minerals carnotite and finchite are hosted in dolomite at the Sulfur Springs Draw deposit, with accessory fluorite, celestine, smectite/illite, autunite, and strontium carbonate. Host carbonate at the Sulfur Springs Draw deposit is ∼190 ka and mineralization mobilized as recently as 3.8 ka. Ash collected near the deposit is 631 ka and erupted from the Yellowstone caldera complex. The Triassic Dockum Group that contains sandstone-hosted uranium deposits throughout the region and underlies the SHP is a potential source for uranium and vanadium. Regional uplift and dissection reintroduced oxygenated groundwater into the Dockum Group, mobilizing uranium. Additional uranium may have been contributed to groundwater by weathering of volcanic ash in Pliocene and Pleistocene host rocks. The locations of the uranium occurrences are mostly in modern drainage systems in the southeast portion of the SHP. Modelling of modern groundwater in the SHP carried out in a parallel study shows that a single fluid could form carnotite through evaporation, and that fluids of the requisite composition are more prevalent in the southern portion of the SHP. The southeastern portion of the SHP hosts more uranium occurrences due to a variety of factors including (1) upward transport of groundwater and connectivity between source and host rock, (2) higher uranium and vanadium content of groundwater, (3) higher rates of groundwater recharge in this region to drive the mineralizing system, and (4) shallower groundwater facilitating surface evaporation. Ongoing erosion of host rocks challenges preservation of deposits and may limit their size. |
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0169-1368 |
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Area |
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Expedition |
|
Conference |
|
|
|
Notes |
|
Approved |
no |
|
|
Call Number |
THL @ christoph.kuells @ hall_calcrete_2019 |
Serial |
124 |
|
Permanent link to this record |