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Lach, P., Cathelineau, M., Brouand, M., & Fiet, N. (2015). In-situ Isotopic and Chemical Study of Pyrite from Chu-Sarysu (Kazakhstan) Roll-front Uranium Deposit. Procedia Earth and Planetary Science, 13, 207–210.
Abstract: Pyrite is common in roll-front type uranium deposit in Chu-sarysu basin, Kazakhstan. Combined in-situ microstructural, isotopic and chemical analysis of pyrite indicates variation in precipitation conditions and in fluid composition. Broad-scale δ34S heterogeneity indicates a complex multi-facet evolution. First generation authigenic framboïdal aggregates are biogenic as demonstrated by the lowest δ34S values of -48‰ to -28‰. The latest generation pyrites are probably hydrothermal with greater δ34S variation (-30‰ to +12‰). This hydrothermal pyrite commonly displays variable enrichment of several trace elements especially As, Co and Ni. Strong variation in δ34S values and variable trace element enrichment is interpreted in terms of continuous variations in fluid composition.
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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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Hebert, B., Baron, F., Robin, V., Lelievre, K., Dacheux, N., Szenknect, S., et al. (2019). Quantification of coffinite (USiO4) in roll-front uranium deposits using visible to near infrared (Vis-NIR) portable field spectroscopy. Journal of Geochemical Exploration, 199, 53–59.
Abstract: Coffinite (USiO4) is a common uranium-bearing mineral of roll-front uranium deposits. This mineral can be identified by the visible near infrared (Vis-NIR) portable field spectrometers used in mining exploration. However, due to the low detection limits and associated errors, the quantification of coffinite abundance in the mineralized sandstones or sandy sediments of roll-front uranium deposits using Vis-NIR spectrometry requires a specific methodological development. In this study, the 1135 nm absorption band area is used to quantify the abundance of coffinite. This absorption feature does not interfere with NIR absorption bands of any other minerals present in natural sands or sandstones of uranium roll-front deposits. The correlation between the 1135 nm band area and coffinite content was determined from a series of spectra measured from prepared mineral mixtures. The samples were prepared with a range of weighted amounts of arenitic sands and synthetic coffinite simulating the range of uranium concentration encountered in roll-front uranium deposits. The methodology presented in this study provides the quantification of the coffinite content present in sands between 0.03 wt% to 1 wt% coffinite with a detection limit as low as 0.005 wt%. The integrated area of the 1135 nm band is positively correlated with the coffinite content of the sand in this range, showing that the method is efficient to quantify coffinite concentrations typical of roll-front uranium deposits. The regression equation defined in this study was then used as a reference to predict the amount of natural coffinite in a set of mineralized samples from the Tortkuduk uranium roll-front deposit (South Kazakhstan).
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Bonnetti, C., Zhou, L., Riegler, T., Brugger, J., & Fairclough, M. (2020). Large S isotope and trace element fractionations in pyrite of uranium roll front systems result from internally-driven biogeochemical cycle. Geochimica et Cosmochimica Acta, 282, 113–132.
Abstract: Complex pyrite textures associated with large changes in isotopic and trace element compositions are routinely assumed to be indicative of multi-faceted processes involving multiple fluid and sulfur sources. We propose that the features of ore-stage pyrite from roll front deposits across the world, revealed in exquisite detail via high-resolution trace element mapping by LA-ICP-MS, reflect the dynamic internal evolution of the biogeochemical processes responsible for sulfate reduction, rather than externally driven changes in fluid or sulfur sources through time. Upon percolation of oxidizing fluids into the reduced host-sandstones, roll front systems become self-organized, with a systematic reset of their activity cycle after each translation stage of the redox interface down dip of the aquifer. Dominantly reducing conditions at the redox interface favor the formation of biogenic framboidal pyrite (δ34S from −30.5 to −12.5‰) by bacterial sulfate reduction and the genesis of the U mineralization. As the oxidation front advances, oxidation of reduced sulfur minerals induces an increased supply of sulfate and metals in solution to the bacterial sulfate reduction zone that has similarly advanced down the flow gradient. Hence, this stage is marked by increased rates of the bacterial sulfate reduction associated with the crystallization of variably As-Co-Ni-Mo-enriched concentric pyrite (up to 10,000′s of ppm total trace contents) with moderately negative δ34S values (from −13.7 to −7.5‰). A final stage of pyrite cement with low trace element contents and heavier δ34S signature (from −6.9 to +18.8‰) marks the end of the roll front activity cycle and the transition from an open to a predominantly closed system behavior (negligible advection of fresh sulfate). Blocky pyrite cement is formed using the remaining sulfate, which now becomes quickly heavy according to a Rayleigh isotope fractionation process. This ends the cycle by depleting the nutrient supplies for the sulfate-reducing bacteria and cementing pore spaces within the host sandstone, effectively restricting fluid infiltration. This internally-driven roll front activity cycle results in systematic, large S isotope and trace element fractionation. Ultimately, the long-time evolution of the basin and fluid sources control the metal endowment and evolution of the system; these events, however, are unlikely to be preserved by the roll front, as a direct result of its hydrodynamic nature.
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Min, M., Xu, H., Chen, J., & Fayek, M. (2005). Evidence of uranium biomineralization in sandstone-hosted roll-front uranium deposits, northwestern China. Ore Geology Reviews, 26(3), 198–206.
Abstract: We show evidence that the primary uranium minerals, uraninite and coffinite, from high-grade ore samples (U3O8\textgreater0.3%) in the Wuyiyi, Wuyier, and Wuyisan sandstone-hosted roll-front uranium deposits, Xinjiang, northwestern China were biogenically precipitated and psuedomorphically replace fungi and bacteria. Uranium (VI), which was the sole electron acceptor, was likely to have been enzymically reduced. Post-mortem accumulation of uranium may have also occurred through physio-chemical interaction between uranium and negatively-charged cellular sites, and inorganic adsorption or precipitation reactions. These results suggest that microorganisms may have played a key role in formation of the sandstone- or roll-type uranium deposits, which are among the most economically significant uranium deposits in the world.
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