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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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Pavelic, P.; Srisuk, K.; Saraphirom, P.; Nadee, S.; Pholkern, K.; Chusanathas, S.; Munyou, S.; Tangsutthinon, T.; Intarasut, T.; Smakhtin, V. |
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Title |
Balancing-out floods and droughts: Opportunities to utilize floodwater harvesting and groundwater storage for agricultural development in Thailand |
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Journal Article |
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2012 |
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Journal of Hydrology |
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470-471 |
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55-64 |
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Water scarcity, Flooding, Drought, Managed aquifer recharge, Floodwater harvesting, Chao Phraya River Basin |
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Summary Thailand’s naturally high seasonal endowment of water resources brings with it the regularly experienced problems associated with floods during the wet season and droughts during the dry season. Downstream-focused engineering solutions that address flooding are vital, but do not necessarily capture the potential for basin-scale improvements to water security, food production and livelihood enhancement. Managed aquifer recharge, typically applied to annual harvesting of wet season flows in dry climates, can also be applied to capture, store and recover episodic extreme flood events in humid environments. In the Chao Phraya River Basin it is estimated that surplus flows recorded downstream above a critical threshold could be harvested and recharged within the shallow alluvial aquifers in a distributed manner upstream of flood prone areas without significantly impacting existing large-medium storages or the Gulf and deltaic ecosystems. Capturing peak flows approximately 1year in four by dedicating around 200km2 of land to groundwater recharge would reduce the magnitude of flooding and socio-economic impacts and generate around USD 250M/year in export earnings for smallholder rainfed farmers through dry season cash cropping without unduly compromising the demands of existing water users. It is proposed that farmers in upstream riparian zones be co-opted as flood harvesters and thus contribute to improved floodwater management through simple water management technologies that enable agricultural lands to be put to higher productive use. Local-scale site suitability and technical performance assessments along with revised governance structures would be required. It is expected that such an approach would also be applicable to other coastal-discharging basins in Thailand and potentially throughout the Asia region. |
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0022-1694 |
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THL @ christoph.kuells @ Pavelic201255 |
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246 |
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Müller, M.; Alaoui, A.; Külls, C.; Leistert, H.; Meusburger, K.; Stumpp, C.; Weiler, M.; Alewell, C. |
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Tracking water pathways in steep hillslopes by δ18O depth profiles of soil water |
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Journal Article |
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2014 |
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Journal of hydrology |
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519 |
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340-352 |
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Elsevier |
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THL @ christoph.kuells @ Mueller2014tracking |
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20 |
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Liesch, T.; Hinrichsen, S.; Goldscheider, N. |
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Uranium in groundwater — Fertilizers versus geogenic sources |
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2015 |
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Science of The Total Environment |
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536 |
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981-995 |
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Drinking water, Fertilizer, Geogenic background, Groundwater, Uranium |
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Due to its radiological and toxicological properties even at low concentration levels, uranium is increasingly recognized as relevant contaminant in drinking water from aquifers. Uranium originates from different sources, including natural or geogenic, mining and industrial activities, and fertilizers in agriculture. The goal of this study was to obtain insights into the origin of uranium in groundwater while differentiating between geogenic sources and fertilizers. A literature review concerning the sources and geochemical processes affecting the occurrence and distribution of uranium in the lithosphere, pedosphere and hydrosphere provided the background for the evaluation of data on uranium in groundwater at regional scale. The state of Baden-Württemberg, Germany, was selected for this study, because of its hydrogeological and land-use diversity, and for reasons of data availability. Uranium and other parameters from N=1935 groundwater monitoring sites were analyzed statistically and geospatially. Results show that (i) 1.6% of all water samples exceed the German legal limit for drinking water (10μg/L); (ii) The range and spatial distribution of uranium and occasional peak values seem to be related to geogenic sources; (iii) There is a clear relation between agricultural land-use and low-level uranium concentrations, indicating that fertilizers generate a measurable but low background of uranium in groundwater. |
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0048-9697 |
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THL @ christoph.kuells @ liesch_uranium_2015 |
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145 |
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Belz, L.; Schüller, I.; Wehrmann, A.; Köster, J.; Wilkes, H. |
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The leaf wax biomarker record of a Namibian salt pan reveals enhanced summer rainfall during the Last Glacial-Interglacial Transition |
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2020 |
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Palaeogeography, Palaeoclimatology, Palaeoecology |
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543 |
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109561 |
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-Alkanes, -Alkanols, Late Quaternary, Organic geochemistry, Palaeohydrology, Southern Africa |
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Conventional continental geoarchives are rarely available in arid southern Africa. Therefore, palaeoclimate data in this area are still patchy and late Quaternary climate development is only poorly understood. In the western Kalahari, salt pans (playas, ephemeral lakes) are common and can feature quasi-continuous sedimentation. This study presents the first climate-related biomarker record using sediments from the Omongwa Pan, a Kalahari salt pan located in eastern Namibia. Our approach to reconstruct vegetation and hydrology focuses on biogeochemical bulk parameters and plant wax-derived lipid biomarkers (n-alkanes, n-alkanols, and fatty acids) and their compound-specific carbon and hydrogen isotopic compositions. The presented record reaches back to 27 ka. During the glacial, rather low δ2H values of n-alkanes and low sediment input exclude a strong influence of winter rainfall. n-Alkane and n-alkanol distributions and δ13C values of n-hentriacontane (n-C31) indicate a shift to a vegetation with a higher proportion of C4 plants at the end of the Last Glacial Maximum until the end of Heinrich Stadial I (ca. 18–14.8 ka), which we interpret to indicate an abrupt excursion to a short wetter period likely to be caused by a temporary southward shift of the Intertropical Convergence Zone. Shifts in δ2H values of n-C31 and plant wax parameters give evidence for changes to drier conditions during early Holocene. Comparison of this dataset with representative continental records from the region points to a major influence of summer rainfall at Omongwa Pan during the regarded time span and demonstrates the potential of southern African salt pans as archives for biomarker-based climate proxies. |
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0031-0182 |
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THL @ christoph.kuells @ belz_leaf_2020 |
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104 |
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