Abstract: In Situ Recovery (ISR) is the most important process of uranium production in the world (50%). It consists of an injection of a leaching solution into a permeable mineralized aquifer (sandstone), pumping of the solution after dissolution of the ore minerals and recovery of the uranium from the pregnant solution in a surface plant. In this context, the fate of swelling clay minerals such as smectites is of main importance due to their role in the mobility of cationic elements by diverse geochemical processes such as ion-exchange reactions or dissolution. The present study details analysis of dioctahedral smectites before and after in-situ leaching by acidic (H2SO4) ISR solutions. Samples were collected from two sedimentary basins hosting some of the main uranium roll front deposits exploited by acidic ISR (Tortkuduk deposit, Shu-Saryssu basin, Kazakhstan, and Dulaan Uul and Zoovch Ovoo deposits, Sainshand basin, Mongolia). Scanning Electron Microscope and X-Ray Diffraction analysis revealed that dioctahedral smectite is a ubiquitous mineral in all analyzed samples, before and after acidification, and revealed a difference of crystal chemistry of the smectites between deposits of Kazakhstan (beidellite type) and Mongolia (montmorillonite type). Chemical analysis and semi-quantification of the smectites before and after acidification also revealed a difference in chemical reactivity, with a higher dissolution of montmorillonite layers compared to beidellite ones, and the importance of ion-exchange reactions. These findings are consistent with literature data obtained on model systems. The persistence of dioctahedral smectites after several years of acidification is crucial for the understanding of geochemical processes during uranium production or remediation of the aquifers. Finally, based on the analysis of samples from U-deposits hosted in both sedimentary basins, a schematic model of the impact of acid solutions on dioctahedral smectite was proposed.

Abstract: The approximate determination of average Ra/U disequilibria in orebodies is one of the most common causes of errors in U reserve estimations. In roll-front deposits, the disequilibria are however frequently distributed following complex geometries, which must be fully understood to prevent major U reserve overestimates and costly unproductive extractive operations. The processes responsible for disruption of the radioactive equilibria and the U and Ra carriers in such complex natural systems remain poorly constrained. In this contribution, we propose an innovative approach, mixing orebody to sub-grain scale studies to unravel the distribution of U and Ra and the processes responsible for their concentration and uncoupling. Using mineral separations, gamma spectrometry and mineral-chemical analyses, we identified the Fe-Ti clusters (altered ilmenite + pyrite/marcasite) as the microsites for coffinite precipitation and Ra concentration. To understand the influence of such clusters on the distribution of U and Ra at the deposit scale, whole-rock Ra/U disequilibria were measured and mapped at a series of ten drill holes along a profile crosscutting the studied roll-front. The main Ra/U disequilibria are encountered around the mineralization in low U content zones. They are controlled by two main processes. (1) In the oxidized zones, the immobility of 230Th with respect to the U produces patches of Ra disequilibria (carried by the altered U minerals). (2) In the immediate vicinity of the roll-front, the dissolution of the mineralization produces an Ra flux trapped by the alteration products of ilmenites, as definitely confirmed by direct SIMS measurements. Such a process is responsible for the Ra disequilibria envelope located downstream of the richest ores, also known as Ra halo. The highest Ra/U ratios correspond to oxidized upstream samples, but most other high Ra/U ratios are from reduced downstream samples close to the mineralization. Such a low to medium U content envelope with high Ra/U ratios constitutes the main cause of U reserve overestimations.

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.