Estimation of uranium endowment by subjective geological analysis—a comparison of methods and estimates for the San Juan Basin,New Mexico

This study investigates how estimates of uranium endowment made by a geologist using an appraisal system that is based upon a formalization of geoscience and decision rules compare with estimates made by informal and unconstrained intuitive processes. The motivation for this study derives from the premise that formalization of decisions would mitigate the heuristic biases and hedging that may result from the use of unconstrained intuitive processes. Estimates of the uranium endowment of the San Juan Basin of New Mexico by four methodologies are compared in this study. These methods, ranked from top to bottom by degree of decomposition (mitigating of heuristic bias)and control on hedging, are as follows Implicit 2 1.5 × 10⁶ s.t. of U₃O₈ Implicit 1 1.6 × 10⁶ s.t. of U₃O₈ NURE (1980) 2.4 × 10⁶ s.t. of U₃O₈ Appraisal system 3.9 × 10⁶ s.t. of U₃O₈ The magnitude of expected uranium endowment estimated by these methods, ranked from smallest to largest, is in this same order. With the exception of the NURE estimates, the magnitude of the variance (uncertainty)of uranium endowment, ranked from smallest to largest, also is in this same order. These results prompt the suggestion that the more decomposed and formalized the estimation procedure, the greater the expected value and the variance of uranium endowment. Equivalently, predicating U ₃ O ₈ endowment estimation strictly upon that part of the geologist's geoscience that is useful in making U ₃ O ₈ endowment estimates and upon his understanding of the region's history produced larger estimates than have previously been reported. However, this method of estimation also shows that uncertainty about the actual state of U ₃ O ₈ endowment is much greater than previously described.     

Enhanced Oxygen Isotope Determination in Uranium Oxides Using BrF5 Fluorination

A new method for accurate determination of oxygen isotopes in uranium oxides encountered in the nuclear fuel cycle was developed using the conventional BrF₅ fluorination technique. Laser‐assisted fluorination was tested for comparison. We focused on fine powders of triuranium octoxide (U₃O₈), uranium dioxide (UO_2±x with 0 ≤ x ≤ 0.25), uranium trioxide (UO₃.nH₂O, with 0.8 ≤ n ≤ 2) and diuranates (M₂U₂O₇.nH₂O, with M = NH₄, Na or Mg_0.5 and 0 ≤ n ≤ 6). Fluorination at room temperature and heating under vacuum at 150 °C are shown to eliminate both adsorbed and structural water from the powder samples. Precision fit for purpose of δ¹⁸O values (± 0.3‰, 1s) and oxygen yields (close to 100%) were obtained for U₃O₈ and UO₂ where oxygen is only bound to uranium. A lower precision was observed for UO₃.nH₂O and M₂U₂O₇.nH₂O where oxygen is both present in the structural H₂O and bonded to uranium and where the extracted O_2(g) can be contaminated by NF₃ and NO_x compounds. Laser‐assisted fluorination gave shifted δ¹⁸O values between +0.8 and +1.4‰ for U₃O₈, around ?0.8‰ for UO₃.nH₂O and between ?3.9 and ?4.5‰ for M₂U₂O₇.nH₂O (± 0.3‰, 1s) compared with the conventional method.     

Determination of the uranium valence state in the brannerite structure using EELS, XPS, and EDX

In this study, the valence states of uranium in synthetic and natural brannerite samples were studied using a combination of transmission electron microscopy-electron energy loss spectroscopy, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) techniques. We used a set of five (UO₂, CaUO₄, SrCa₂UO₆, UTi₂O₆, and Y_0.5U_0.5Ti₂O₆) U standard samples, including two synthetic brannerites, to calibrate the EELS branching ratio, M₅/(M₄ +M₅), against the number of f electrons. The EELS data were collected at liquid nitrogen temperature in order to minimise the effects of electron beam reduction of U⁶⁺ and U⁵⁺. Test samples consisted of three additional synthetic brannerites (Th_0.7U_0.3Ti₂O₆, Ca_0.2U_0.8Ti₂O₆, and Th_0.55U_0.3Ca_0.15Ti₂O₆) and three natural brannerites from different localities. The natural brannerite samples are all completely amorphous, due to cumulative alpha decay events over geological time periods (24–508 Ma). Our U valence calibration results are in reasonable agreement with previous work, suggesting possibly a non-linear relationship between the branching ratio and the number of f electrons (and hence the average valence state) of U in solids. We found excellent agreement between the nominal valence states of U and the average valence states determined directly by EELS and estimated by EDX analysis (with assumptions regarding stoichiometry) in two of the three synthetic brannerite test samples. The average U oxidation states of the five synthetic brannerite samples, as derived from XPS analyses, are also in good agreement with those determined by other techniques. The average valence states of U in three amorphous (metamict) natural brannerite samples with alpha decay doses ranging from 3.6×10¹⁶ to 6.9×10¹⁷ /mg were found to be 4.4, 4.7, and 4.8, consistent with the presence of U⁵⁺ and/or U⁶⁺ as well as U⁴⁺ in these samples. These results are in general agreement with previous wet chemical analyses of natural brannerite. However, the average valence states inferred by SEM-EDX for two of the natural brannerite samples do not show satisfactory agreement with the EELS determined valence. This may be due to the occurrence of OH^– groups, cation vacancies, anion vacancies, or excess oxygen in the radiation-damaged structure of natural brannerite.     

澳大利亚兰杰一号铀矿之生命周期：地质、资源、生产与修复

兰杰一号铀矿及其所属的鳄鱼河铀矿田产于北澳太古宙克拉通内古元古代裂谷背景下发展起来的松溪造山带,矿体产于新太古代—古元古代结晶-变质基底/晚古元古代—中元古代康博尔吉红层建造不整合界面之下,铀矿化分3个时代,U_1为1720～1680Ma,U_2为1420～1040Ma,U_3为474±6Ma,U1是主矿化时代。该矿床于1969年后期通过航空放射性测量被发现,1970’s经勘探圈定了No.1和No.3两个铀矿体,总计资源储量124681t@0.23%U_3O_8。1980年10月正式露采,至2018年12月,总计生产了128739t U_3O_8。1985财年开始,ERA(澳大利亚能源资源有限责任公司)向世界核能市场共计销售了产于兰杰铀矿的119882t U_3O_8。2009年,发现了No.3深部矿,探明资源储量为43857t@0.22%U_3O_8,这部分资源将以地下开采方式利用。预计到2026年,采区地貌景观和生态环境将得到恢复。进一步讨论了澳北元古宙不整合面型铀矿找矿的方向,持续稳定的铀矿开采与生产的意义,以及投资澳大利亚铀矿业需要注意的政治与法律问题。这些内容可以为国内矿业企业及地勘单位合理部署澳洲铀矿勘查与开发提供参考。     

A study of synthetic and natural uranium oxides by X-ray photoelectron spectroscopy

Synthetic and natural uranium oxides UO _x (2≦×≦3) have been studied with X-ray photoelectron spectroscopy (XPS) to determine the phase composition and content of uranium ions in uraninites with a varying degree of oxidation. A strong hybridization of U_6p and O_2s orbitals has been found which permits a quantitative assessment of the U-O bond lengths. The values of such bonds in some substances have been found to be smaller than those in synthetic U(VI) oxide. The oxides U₂O₅ and U₃O₈ contain two types of uranium ions with a varying degree of oxidation.     

Occurrence of uranium in metasedimentary enclaves within basement granite, near Peddur and Kottur, Karimnagar District, Andhra Pradesh

Several radioactive anomalies due to uranium and thorium, associated with the mesedimentary enclaves (Archaean) within granite (Archaean to Early-Proterozoic) have been recorded in parts of Karimnagar Granulite Terrain, Karimnagar Dist. At Peddur and Kottur, Uraninite has been identified in the samples of metasediments. The metasediment from these two places have been subjected to granulite facies of metamorphism and host high values of uranium with negligible thorium. In Peddur, samples of metasediments have assayed as high as 1.96% U₃O₈ with negligible thorium, and in Kottur up to 0.059% U₃O₈. Leaching studies on these samples have indicated that most of the U₃O₈ present is leachable. This discovery has opened up the possibility of finding uranium mineralisation in Archaean metasediments and thus provides a thrust for uranium exploration in similar geological environs in India. Further, the basement granite along with the metasedimentary enclaves has the potential to act as a provenance for a possible unconformity type or sandstone type U-deposit in the rocks of overlying Pakhal and Gondwana Supergroup, in Pranhita-Godavari Basin, situated to the east of this area.     

Heterogeneous reduction of U by structural Fe from theory and experiment

Computational and experimental studies were performed to explore heterogeneous reduction of U⁶⁺ by structural Fe²⁺ at magnetite (Fe₃O₄) surfaces. Molecular Fe-Fe-U models representing a uranyl species adsorbed in a biatomic bidentate fashion to an iron surface group were constructed. Various possible charge distributions in this model surface complex were evaluated in terms of their relative stabilities and electron exchange rates using ab initio molecular orbital methods. Freshly-cleaved, single crystals of magnetite with different initial Fe²⁺/Fe³⁺ ratios were exposed to uranyl-nitrate solution (pH ∼ 4) for 90 h. X-ray photoelectron spectroscopy and electron microscopy indicated the presence of a mixed U⁶⁺/U⁵⁺ precipitate heterogeneously nucleated and grown on stoichiometric magnetite surfaces, but only the presence of sorbed U⁶⁺ and no precipitate on sub-stoichiometric magnetite surfaces. Calculated electron transfer rates indicate that sequential multi-electron uranium reduction is not kinetically limited by conductive electron resupply to the adsorption site. Both theory and experiment point to structural Fe²⁺ density, taken as a measure of thermodynamic reducing potential, and sterically accessible uranium coordination environments as key controls on uranium reduction extent and rate. Uranium incorporation in solid phases where its coordination is constrained to the uranate type should widen the stability field of U⁵⁺ relative to U⁶⁺. If uranium cannot acquire 8-fold coordination then reduction may proceed to U⁵⁺ but not necessarily U⁴⁺.     

Raman spectroscopy and heat capacity measurement of calcium ferrite type MgAl2O4 and CaAl2O4

Raman spectroscopy of calcium ferrite type MgAl₂O₄ and CaAl₂O₄ and heat capacity measurement of CaAl₂O₄ calcium ferrite were performed. The heat-capacity of CaAl₂O₄ calcium ferrite measured by a differential scanning calorimeter (DSC) was represented as C_P(T)=190.6–1.116 × 10⁷T^–2 + 1.491 × 10⁹T^–3 above 250 K (T in K). The obtained Raman spectra were applied to lattice dynamics calculation of heat capacity using the Kieffer model. The calculated heat capacity for CaAl₂O₄ calcium ferrite showed good agreement with that by the DSC measurement. A Kieffer model calculation for MgAl₂O₄ calcium ferrite similar to that for CaAl₂O₄ calcium ferrite was made to estimate the heat capacity of the former. The heat capacity of MgAl₂O₄ calcium ferrite was represented as C_P(T)=223.4–1352T ^–0.5 – 4.181 × 10⁶T ^–2 + 4.300 × 10⁸T ^–3 above 250 K. The calculation also gave approximated vibrational entropies at 298 K of calcium ferrite type MgAl₂O₄ and CaAl₂O₄ as 97.6 and 114.9 J mol^–1 K^–1, respectively.     

The mobility of U and Th in subduction zone fluids: an indicator of oxygen fugacity and fluid salinity

The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO₂ buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO₂ + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO₂ is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, D^fluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.     

Transformation of synthetic U3O8 into different uranium oxide hydrates

Summary Referring to the natural formation of secondary uranium minerals, the primary transformation of U₃O₈ into schoepite has been investigated. The transformation is realized in a continuous system with O₂, CO₂ and H₂O. At 100°C schoepite III, UO₃ · zH₂O (z 1), is formed (a = 14.12; b = 16.83; c = 15.22 Å) with a density of 4.460 g/cm³. At 25°C a mixture of schoepite II (UO₃ · yH₂O, 1 < y < 2; a = 13.99; b = 16.72; c = 14.73 Å) and schoepite I (UO₃ · xH₂O, x 2; a = 14.33; b = 16.79; c = 14.73 Å) is obatined. From thermogravimetric analysis the activation energy of dehydration for schoepite III is determined as 49(3) · 10³ J/mole.

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Umwandlung von synthetischem U₃O₈ in verschiedene Uranoxidhydrate

Zusammenfassung In Hinblick auf die natürliche Bildung sekundärer Uranminerale wurde die primäre Umwandlung von U₃O₈ in Schoepit untersucht. Die Umwandlung wurde in einem kontinuierlichen System mit O₂, CO₂ und H₂O bewerkstelligt. Bei 100°C bildet sich Schoepit III (UO₃ · zH₂O, z 1; a = 14.12, b = 16.83, c = 15.22 Å; Dichte: 4.460 g/cm³). Bei 25°C wird eine Mischung von Schoepit II (UO₃ · yH₂O, 1 < y < 2; a = 13.99, b = 16.72, c = 14.73 Å) und Schoepit I (UO₃ · xH₂O, x 2; a = 14.33, b = 16.79, c = 14.73 Å) erhalten. Aus der thermogravimetrischen Analyse wurde die Aktivierungsenergie der Dehydratation von Schoepit III mit 49(3) · 10³ J/mole berechnet.

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Who wishes to dedicate the paper to the memory of his father, Hendrik Vochten.

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With 3 Figures