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Brook, G. A., Marais, E., Srivastava, P., & Jordan, T. (2007). Timing of lake-level changes in Etosha Pan, Namibia, since the middle Holocene from OSL ages of relict shorelines in the Okondeka region. Quaternary International, 175(1), 29–40.
Abstract: In 2003 examination of aerial photographs revealed a series of previously unknown relict shorelines on the arcuate ridge, possibly a clay lunette dune, that marks the western boundary of Etosha Pan in Namibia. The shorelines are 120–600m wide and the most prominent extend for tens of km around the lunette dune. The shorelines were examined on the ground in 2004 and an attempt was made to date the three lowest levels at ca. 5, 2.5 and 1m above the present pan surface. The OSL ages obtained indicate higher and more prolonged lake conditions than today at ca. 6.4, 4.0 and 2.1ka with the youngest shoreline sediments resting on an ancient pan surface dating to ca. 13ka. The evidence indicates dry conditions in the pan at ca. 13ka, wetter conditions and higher lake levels in the middle Holocene followed by a decline in lake levels to the present. Periods of inundation were of sufficient duration to produce shorelines at the southwestern end of the pan due to the prevailing northeasterly winds that would have maximized wave action along this section of the pan margin. The Etosha findings, together with other regional paleoclimate data, suggest four periods of increased wetness in SW Africa during the Holocene at 7–5, 4.5–3.5, 2.5–1.7 and ca. 1.0ka. There is widespread evidence for the oldest of these periods suggesting that it was a prominent and widespread interval of wetness. Prior to ca. 8.0ka the climate may have been drier than today.
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Etschmann, B., Liu, W., Li, K., Dai, S., Reith, F., Falconer, D., et al. (2017). Enrichment of germanium and associated arsenic and tungsten in coal and roll-front uranium deposits. Chemical Geology, 463, 29–49.
Abstract: 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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Ammar, F. H., Deschamps, P., Chkir, N., Zouari, K., Agoune, A., & Hamelin, B. (2020). Uranium isotopes as tracers of groundwater evolution in the Complexe Terminal aquifer of southern Tunisia. Quaternary International, 547, 33–49.
Abstract: 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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Hamutoko, J., Mapani, B., Ellmies, R., Bittner, A., & Külls, C. (2014). A fingerprinting method for the identification of uranium sources in alluvial aquifers: An example from the Khan and Swakop Rivers, Namibia. Physics and Chemistry of the Earth, Parts A/B/C, 72, 34–42.
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Grodek, T., Enzel, Y., Morin, E., Jacoby, Y., Dahan, O., Benito, G., et al. (2008). Flood hydrology, flood routing, paleohydrology and the estimation of water resources along the shallow alluvial aquifers of the Kuiseb River, Namibia. In Abstracts – Israel Geological Society (Vol. 2008, 37).
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