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Smedley, P. L., Bearcock, J. M., Ward, R. S., Crewdson, E., Bowes, M. J., Darling, W. G., et al. (2023). Monitoring of methane in groundwater from the Vale of Pickering, UK: Temporal variability and source discrimination. Chemical Geology, 636, 121640.
Abstract: Groundwater abstracted from aquifers in the Vale of Pickering, North Yorkshire, UK and monitored over the period 2015–2022, shows evidence of variable but commonly high concentrations of dissolved CH4. Sampled groundwater from the Jurassic organic-rich Kimmeridge Clay Formation (boreholes up to 180 m depth) has concentrations up to 57 mg/L, and concentrations up to 59 mg/L are found in groundwater from underlying confined Corallian Group limestone (borehole depths 50–227 m). The high concentrations are mainly from boreholes in the central parts of the vale. Small concentrations of ethane (C2H6, up to 800 μg/L) have been found in the Kimmeridge Clay and confined Corallian groundwaters, and of propane (C3H8, up to 160 μg/L) in deeper boreholes (110–180 m) from these formations. The concentrations are typically higher in groundwater from the deeper boreholes and vary with hydrostatic pressure, reflecting the pressure control on CH4 solubility. The occurrences contrast with groundwater from shallow Quaternary superficial deposits which have low CH4 concentrations (up to 0.39 mg/L), and with the unconfined and semi-confined sections of the Corallian aquifer (up to 0.7 mg/L) around the margins of the vale. Groundwater from the Quaternary, Kimmeridge Clay formations and to a small extent the confined Corallian aquifer, supports local private-water supplies, that from the peripheral unconfined sections of Corallian also supports public supply for towns and villages across the region. Dissolved methane/ethane (C1/C2) ratios and stable-isotopic compositions (δ13C-CH4, δ2H-CH4 and δ13C-CO2) suggest that the high-CH4 groundwater from both the Kimmeridge Clay and confined Corallian formations derives overwhelmingly from biogenic reactions, the methanogenesis pathway by CO2 reduction. A small minority of groundwater samples shows a more enriched δ13C-CH4 composition (−50 to −44 ‰) which has been interpreted as due to anaerobic or aerobic methylotrophic oxidation in situ or post-sampling oxidation, rather than derivation by a thermogenic route. Few of the existing groundwater sites are proximal to abandoned or disused conventional hydrocarbon wells that exist in the region, and little evidence has been found for an influence on groundwater dissolved gases from these sites. The Vale of Pickering has also been under recent consideration for development of an unconventional hydrocarbon (shale-gas) resource. In this context, the monitoring of dissolved gases has been an important step in establishing the high-CH4 baseline of groundwaters from Jurassic deposits in the region and in apportioning their sources and mechanisms of genesis.
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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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Prusty, S., Somu, P., Sahoo, J. K., Panda, D., Sahoo, S. K., Sahoo, S. K., et al. (2022). Adsorptive sequestration of noxious uranium (VI) from water resources: A comprehensive review. Chemosphere, 308, 136278.
Abstract: Groundwater is usually utilized as a drinking water asset everywhere. Therefore, groundwater defilement by poisonous radioactive metals such as uranium (VI) is a major concern due to the increase in nuclear power plants as well as their by-products which are released into the watercourses. Waste Uranium (VI) can be regarded as a by-product of the enrichment method used to produce atomic energy, and the hazard associated with this is due to the uranium radioactivity causing toxicity. To manage these confronts, there are so many techniques that have been introduced but among those adsorptions is recognized as a straightforward, successful, and monetary innovation, which has gotten major interest nowadays, despite specific drawbacks regarding operational as well as functional applications. This review summarizes the various adsorbents such as Bio-adsorbent/green materials, metal oxide-based adsorbent, polymer based adsorbent, graphene oxide based adsorbent, and magnetic nanomaterials and discuss their synthesis methods. Furthermore, this paper emphasis on adsorption process by various adsorbents or modified forms under different physicochemical conditions. In addition to this adsorption mechanism of uranium (VI) onto different adsorbent is studied in this article. Finally, from the literature reviewed conclusion have been drawn and also proposed few future research suggestions.
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Lartigue, J. E., Charrasse, B., Reile, B., & Descostes, M. (2020). Aqueous inorganic uranium speciation in European stream waters from the FOREGS dataset using geochemical modelling and determination of a U bioavailability baseline. Chemosphere, 251, 126302.
Abstract: The concentration of the bioavailable uranium fraction (Ubio) at the European scale was deduced by geochemical modelling considering several definitions found in the literature and the FOREGS European stream waters geochemical atlas dataset to produce a Ubio baseline. A sensitivity analysis was performed using three thermodynamic databases. We also investigated the link between total dissolved uranium (Uaq) concentrations, speciation and global stream water chemistry on the one hand, and the lithology and ages of the surrounding rocks on the other. The more U-enriched the stream sediments or rock type contexts are, which tends to be the case with rocks containing silicates (4.1 mg/kg), the less U-concentrated the stream waters are (0.15 μg/L). Sedimentary rocks lead to slightly higher Uaq concentrations (0.34 μg/L) even if the concentration in sediment (Used) is relatively low (1.6 mg/kg). This trend is reversed for Ubio, with higher concentrations in a crystalline context. The mean estimated Ubio value ranges from 1.5.10−3 to 65.3 ng/L and can fluctuate by 3 orders of magnitude depending on the considered definition as opposed to by 2 orders of magnitude accountable to differences between thermodynamic databases. The classification of the water in relation to the two surrounding rock lithologies makes it possible to reduce the mean variability for the Ubio concentrations. Irrespective of the definition of Ubio considered, in 59% of cases the Ubio fraction represents less than 1% of Uaq. Several threshold values relating to Ubio were proposed, assuming knowledge only of the aqueous concentrations of the major elements and Uaq.
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Veerasamy, N., Kasar, S., Murugan, R., Inoue, K., Natarajan, T., Ramola, R. C., et al. (2023). 234U/238U disequilibrium and 235U/238U ratios measured using MC-ICP-MS in natural high background radiation area soils to understand the fate of uranium. Chemosphere, 323, 138217.
Abstract: The Chhatrapur-Gopalpur coastal area in Odisha, India is a well-known natural high background radiation (HBRA) area due to the abundance of monazite (a thorium bearing radioactive mineral) in beach sands and soils. Recent studies on Chhatrapur-Gopalpur HBRA groundwater have reported high concentrations of uranium and its decay products. Therefore, the soils of the Chhatrapur-Gopalpur HBRA are reasonably suspected as the sources of these high uranium concentrations in groundwater. In this report, first the uranium concentrations in soil samples were measured using inductively coupled plasma mass spectrometry (ICP-MS) and they were found to range from 0.61 ± 0.01 to 38.59 ± 0.16 mg kg−１. Next, the 234U/238U and 235U/238U isotope ratios were measured to establish a baseline for the first time in Chhatrapur-Gopalpur HBRA soil. Multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) was used for measurement of these isotope ratios. The 235U/238U ratio was observed to be the normal terrestrial value. The 234U/238U activity ratio, was calculated to understand the secular equilibrium between 234U and 238U in soil and it varied from 0.959 to 1.070. To understand the dynamics of uranium in HBRA soil, physico-chemical characteristics of soil were correlated with uranium isotope ratios and this correlation of 234U/238U activity ratio indicated the leaching of 234U from Odisha HBRA soil.
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