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.

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.

Abstract: More than 2.5 billion people depend upon groundwater worldwide for drinking, and giving quality water has become one of the great apprehensions of human culture. The contamination of Uranium (U) and Arsenic (As) in the groundwater of India is gaining global attention. The current review provides state-of-the-art groundwater contamination with U and As in different zones of India based on geology and soil texture. The average concentration of U in different zones of India was in the order: West Zone (41.07 μg/L) \textgreater North Zone (37.7 μg/L) \textgreater South Zone (13.5 μg/L)\textgreater Central Zone (7.4 μg/L) \textgreater East Zone (5.7 μg/L) \textgreaterSoutheast Zone (2.4 μg/L). The average concentration of As in groundwater of India is in the order: South Zone (369.7 μg/L)\textgreaterCentral Zone (260.4 μg/L)\textgreaterNorth Zone (67.7 μg/L)\textgreaterEast Zone (60.3 μg/L)\textgreaterNorth-east zone (9.78 μg/L)\textgreaterWest zone (4.14 μg/L). The highest concentration of U and As were found in quaternary sediments, but U in clay skeletal and As in loamy skeletal. Results of health risk assessment showed that the average health quotient of U in groundwater for children and adults was less than unity. In contrast, it was greater than unity for As posing a harmful impact on human health. This review provides the baseline data regarding the U and As contamination status in groundwater of India, and appropriate, effective control measures need to be taken to control this problem.