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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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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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Boulesteix, T., Cathelineau, M., Deloule, E., Brouand, M., Toubon, H., Lach, P., et al. (2019). Ilmenites and their alteration products, sinkholes for uranium and radium in roll-front deposits after the example of South Tortkuduk (Kazakhstan). Journal of Geochemical Exploration, 206, 106343.
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.
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Grozeva, N. G., Radwan, J., Beaucaire, C., & Descostes, M. (2022). Reactive transport modeling of U and Ra mobility in roll-front uranium deposits: Parameters influencing 226Ra/238U disequilibria. Journal of Geochemical Exploration, 236, 106961.
Abstract: Uranium reserve estimates in ore deposits can be significantly impacted by 226Ra/238U disequilibria arising from the differential mobility of uranium and radium during groundwater transport. 1D reactive transport models were developed to investigate the long-term effects of retention processes (UO2(am) precipitation, U(VI) and Ra sorption on smectite, Ra co-precipitation with barite) on the repartitioning of 238U and 226Ra during formation of roll-front type deposits. Analytical solutions to radioactive decay chains were used in complement to examine the influence of geochemical parameters, including fluid 234U/238U activity ratios and α-recoil loss, on 226Ra/238U disequilibria in uranium ores. Model results demonstrate that smectite and barite can produce 226Ra/238U ratios \textgreater1 at low uranium contents and may explain 226Ra/238U disequilibria occurring in altered rock up- and downstream of roll-front deposits. The capacity of these phases to take up Ra and generate 226Ra/238U disequilibria depends on both mineral contents and groundwater compositions, and is thus expected to be site-specific. Simulations of ore deposits that advance downstream with time demonstrate the formation of stronger 226Ra/238U disequilibria, as expected, in the downgradient side or nose of the ore, reflecting both younger mineralization ages and the presence of active uranium precipitation. Whether disequilibria are positive or negative with respect to secular equilibrium, however, depends on the 234U/238U activity ratio in the fluid from which uranium minerals precipitate. Smaller hydraulic conductivities are shown to generate a narrower range in 226Ra/238U activity ratios with distance, and may explain the occurrence of disequilibria in the limb ore that are less pronounced than those in the nose. Furthermore, the ability of α-recoil loss to decrease 226Ra/238U activity ratios at secular equilibrium may account for negative disequilibria in high grade ores. The South Tortkuduk uranium deposits (Kazakhstan) are subsequently used as a case study to identify the processes and parameters that may contribute to 226Ra/238U disequilibria at this site. Variations in multiple parameters, including clay contents, barite contents, and mineralization ages, are found to reproduce measured 226Ra/238U activity ratios in the roll-front ore. Prioritization of these parameters will necessitate field measurements targeting both groundwater fluids and the host rock. Results from this study will ultimately aid geologists in building appropriate hydrogeochemical data sets to more efficiently locate and exploit uranium ore deposits.
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Robin, V., Beaufort, D., Tertre, E., Reinholdt, M., Fromaget, M., Forestier, S., et al. (2020). Fate of dioctahedral smectites in uranium roll front deposits exploited by acidic In Situ Recovery (ISR) solutions. Applied Clay Science, 187, 105484.
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.
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Hubbard, B. E., Gallegos, T. J., Stengel, V., Hoefen, T. M., Kokaly, R. F., & Elliott, B. (2024). Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain. Journal of Geochemical Exploration, 257, 107370.
Abstract: VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey’s (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA. Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite. Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data. The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.
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Jroundi, F., Descostes, M., Povedano-Priego, C., Sánchez-Castro, I., Suvannagan, V., Grizard, P., et al. (2020). Profiling native aquifer bacteria in a uranium roll-front deposit and their role in biogeochemical cycle dynamics: Insights regarding in situ recovery mining. Science of The Total Environment, 721, 137758.
Abstract: A uranium-mineralized sandy aquifer, planned for mining by means of uranium in situ recovery (U ISR), harbors a reservoir of bacterial life that may influence the biogeochemical cycles surrounding uranium roll-front deposits. Since microorganisms play an important role at all stages of U ISR, a better knowledge of the resident bacteria before any ISR actuations is essential to face environmental quality assessment. The focus here was on the characterization of bacteria residing in an aquifer surrounding a uranium roll-front deposit that forms part of an ISR facility project at Zoovch Ovoo (Mongolia). Water samples were collected following the natural redox zonation inherited in the native aquifer, including the mineralized orebody, as well as compartments located both upstream (oxidized waters) and downstream (reduced waters) of this area. An imposed chemical zonation for all sensitive redox elements through the roll-front system was observed. In addition, high-throughput sequencing data showed that the bacterial community structure was shaped by the redox gradient and oxygen availability. Several interesting bacteria were identified, including sulphate-reducing (e.g. Desulfovibrio, Nitrospira), iron-reducing (e.g. Gallionella, Sideroxydans), iron-oxidizing (e.g. Rhodobacter, Albidiferax, Ferribacterium), and nitrate-reducing bacteria (e.g. Pseudomonas, Aquabacterium), which may also be involved in metal reduction (e.g. Desulfovibrio, Ferribacterium, Pseudomonas, Albidiferax, Caulobacter, Zooglea). Canonical correspondence analysis (CCA) and co-occurrence patterns confirmed strong correlations among the bacterial genera, suggesting either shared/preferred environmental conditions or the performance of similar/complementary functions. As a whole, the bacterial community residing in each aquifer compartment would appear to define an ecologically functional ecosystem, containing suitable microorganisms (e.g. acidophilic bacteria) prone to promote the remediation of the acidified aquifer by natural attenuation. Assessing the composition and structure of the aquifer’s native bacteria is a prerequisite for understanding natural attenuation and predicting the role of bacterial input in improving ISR efficiency.
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Rallakis, D., Michels, R., Cathelineau, M., Parize, O., & Brouand, M. (2021). Conditions for uranium biomineralization during the formation of the Zoovch Ovoo roll-front-type uranium deposit in East Gobi Basin, Mongolia. Ore Geology Reviews, 138, 104351.
Abstract: The Zoovch Ovoo uranium roll-front-type deposit is hosted in the Sainshand Formation, a Late Cretaceous siliciclastic reservoir, which constitutes the upper part of the post-rift infilling of the Mesozoic East Gobi Basin in SE Mongolia. The Sainshand Formation consists of unconsolidated medium-grained sand, silt and clay intervals deposited in fluvial-lacustrine settings. The uranium deposit is confined within a 60–80 m thick siliciclastic sequence inside aquifer-driven systems. The overall system experienced shallow burial and was never subjected to temperatures higher than 40 °C. This study proposes a comprehensive metallogenic model for this uranium deposit. Sedimentological and mineralogical observations from drill core samples to the microscopic scale (optical and Scanning Electron Microscopy) together with in situ geochemistry of late-formed phases (Laser Ablation–Inductively Coupled Plasma Mass Spectrometry, Electron Probe Microanalysis, Fourier Transform–Infrared Spectroscopy) were considered for the reconstruction of the main stages of U trapping. In the mineralized zone, the uranium ore is expressed as Ca–enriched uraninite (UO2) and less commonly as Ca–enriched phospho-coffinite (U, P)SiO4. Trapping mechanisms include i) complexation (i.e. uranyl-carboxyl complexes), ii) adsorption on organic or clay particles) and iii) reduction by pyrite and by bacterial activity to amorphous uraninite. In all cases, the organic matter plays either the role of trap for uranium or nutrient for bacteria that can trap uranium through their metabolism. The shallow burial diagenesis conditions do not allow direct reduction of U(VI) by organic carbon. The δ34S values of the iron disulfide are very diverse, fluctuating in extreme cases between −50 to + 50‰, with an average δ34S value for framboidal pyrite at 2‰, and −20‰ for euhedral pyrite. The positive and negative values reflect close versus open fractionation systems, while bacterial sulphate reduction (BSR) is active during the whole diagenetic history of the deposit as an essential source of reduced sulfur. Therefore, using detrital organic matter as a carbon source, microorganisms play a significant role in uranium trapping, either as a direct reducing agent for uranium or pyrite formation, which will trap uranium through redox driven epigenetic processes.
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Min, M., Chen, J., Wang, J., Wei, G., & Fayek, M. (2005). Mineral paragenesis and textures associated with sandstone-hosted roll-front uranium deposits, NW China. Ore Geology Reviews, 26(1), 51–69.
Abstract: We present a first paragenetic study of the Wuyier, Wuyisan, Wuyiyi and Shihongtan sandstone-hosted roll-front uranium deposits, northwest China. The mineralization is hosted by Lower–Middle Jurassic coarse- to medium-grained sandstones, which are dark-gray to black due to a mixture of ore minerals and carbonaceous debris. The sandstone is alluvial fan-braided river facies. Minerals associated with these deposits can be broadly categorized as detrital, authigenic, and ore-stage mineralization. Ore minerals consist of uraninite and coffinite. This is the first noted occurrence of coffinite in this type of deposit in China. Sulfide minerals associated with the uranium minerals are pyrite, marcasite, and less commonly, sphalerite and galena. The sulfide minerals are largely in textural equilibrium with the uranium minerals. However, these sulfide minerals occasionally appear to predate, as well as postdate, the uranium minerals. This implies that there are multiple generations of sulfides associated with these deposits. The ore minerals occur interstitially between fossilized wood cells in the sandstones as well as replace fossilized wood and biotite. The deposits are generally low-grade. Primary uranium minerals associated with the low-grade deposits are generally too small, ranging from 0.2 to 0.3 μm in diameter, to be observed by optical microscopy and are only observed by electron microscopy. Mineral paragenesis and textures indicate that these deposits formed under low temperature (30–50 °C) conditions.
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Pham, Q. - N., Nguyen, T. - C., Ta, T. - T., & Tran, T. - L. (2023). Comprehensive approach to sustainable groundwater management in semi-arid Ninh Thuan plain, Vietnam. Groundwater for Sustainable Development, 23, 101031.
Abstract: Vietnam is a country with a long coastline and a high population density residing in the coastal plains. The largest dry area in Vietnam, the coastal plain of Ninh Thuan province, always lacks water in the first dry months of the year (Jan., Feb., Mar., and Apr.). Groundwater is an extremely valuable resource for supplies at this time. Therefore, the objective of this study is to establish a comprehensive approach to sustainable groundwater management in this semi-arid region. This approach is not only mitigating the negative impacts of factors such as climate change, sea level rise, and socio-economic development but also suggesting measures for management of aquifer recharge. A groundwater model for a 3-layer system with variable density flow SEAWAT is built to predict the impacts of climate change and sea level rise without a change in groundwater abstraction. This model helps to understand the trend of salt intrusion and lowering groundwater level in the study area. Afterwards, scenarios with different ground water abstraction and groundwater development such as ground dam, infiltration basin have been set up to meet the demands of socio-economic development in the future. Predicted results will show the impacts of the groundwater systems in the area such as groundwater level change, and saltwater intrusion. Controlled groundwater abstraction and some measures of groundwater development such as infiltration basin, underground dam would allow for an increase of up to 50000m3/day in the year 2050 without negative impacts on the aquifer system.
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