Uranium minerals from the San Marcos District, Chihuahua, Mexico

The mineralogy of the two uranium deposits (Victorino and San Marcos I) of Sierra San Marcos, located 30 km northwest of Chihuahua City, Mexico, was studied by optical microscopy, powder X-ray diffraction with Rietveld analysis, scanning electron microscopy with energy dispersive X-ray analysis, inductively coupled plasma spectrometry, and gamma spectrometry. At the San Marcos I deposit, uranophane Ca(UO₂)₂Si₂O₇·6(H₂O) (the dominant mineral at both deposits) and metatyuyamunite Ca(UO₂)(V₂O₈)·3(H₂O) were observed. Uranophane, uraninite (UO_2+x), masuyite Pb(UO₂)₃O₃(OH)·3(H₂O), and becquerelite Ca(UO₂)₆O₄(OH)₆ ·(8H₂O) are present at the Victorino deposit. Field observations, coupled with analytical data, suggest the following sequence of mineralization: (1) deposition of uraninite, (2) alteration of uraninite to masuyite, (3) deposition of uranophane, (4) micro-fracturing, (5) calcite deposition in the micro-fractures, and (6) formation of becquerelite. The investigated deposits were formed by high-to low-temperature hydrothermal activity during post-orogenic evolution of Sierra San Marcos. The secondary mineralization occurred through a combination of hydrothermal and supergene alteration events. Becquerelite was formed in situ by reaction of uraninite with geothermal carbonated solutions, which led to almost complete dissolution of the precursor uraninite. The Victorino deposit represents the second known occurrence of becquerelite in Mexico, the other being the uranium deposits at Peña Blanca in Chihuahua State.     

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H₂O)₅[(UO₂)(SiO₃(OH)]₂, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb²⁺-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl₂-HCl solution of pH 2. They are part of an aged silica coating of composition Si₂O₂(OH)₄(H₂O)_n. An amorphous layer forms on the surface of uranophane in a MgCl₂-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO₃)₂-HCl and BaCl₂-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO₃)₂-HCl < BaCl₂-HCl < CaCl₂-HCl < HCl < SrCl₂-HCl < MgCl₂-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl⁺).     

A Critical Evaluation of U–Pb Calibration Schemes Used in SIMS Zircon Geochronology

Precision and accuracy in SIMS zircon geochronology strongly depend on the method of determination of the interelement ion ratios (e.g., ²⁰⁶Pb/²³⁸U) from the measured secondary ion ratios (²⁰⁶Pb⁺/²³⁸U⁺). Six possible U–Pb calibrations (Pb/U–UO₂/U, Pb/U–UO/U, Pb/U–UO₂/UO, Pb/UO–UO₂/U, Pb/UO–UO/U, Pb/UO–UO₂/UO) based on simple power law relationships, and Pb/UO₂‐related one‐ and two‐ (a power law) dimensional ones were compared using data acquired on the 91500 zircon reference material from one hundred measurement sessions, to determine the most statistically reliable scheme. Taking advantage of U oxide species (UO and UO₂) over atomic U, due to their similar energy distribution to Pb and higher intensities, the data calibrated with Pb/UO–UO₂/UO showed the smallest mean uncertainties and dispersions, and provided the best‐fit calibration curve consistently. Although it was demonstrated with Temora 2 that the unknown zircon age was not changed significantly by different calibrations, its precision could be improved using the Pb/UO–UO₂/UO calibration in zircon geochronology.     

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.     

High and low temperature alteration of uranium and thorium minerals, Um Ara granites, south Eastern Desert, Egypt

The Um Ara area, in the south Eastern Desert of Egypt contains a number of uranium occurrences related to granitic rocks. U-rich thorite, thorite and zircon are the main primary uranium- and thorium-bearing minerals found in mineralized zones of the Um Ara alkali-feldspar granites; uranophane is the most common secondary uranium mineral. U-rich thorite contains blebs of galena, has rims of uranophane and contains inclusions of Zr-rich thorite. Electron probe microanalysis (EPMA) provides an indication of a range of solid solution between thorite and zircon, in which intermediate phases, such as Th-rich zircon and Zr-rich thorite, were formed. These phases have higher sum of all cations per formula (2.05 to 2.06 apfu, for 4 oxygen atoms) than that of ideal thorite and zircon. This is attributed to the presence of substantial amount of interstitial cations such as Ca, U and Al in these phases. Some zircon grains are stoichiometric in composition, other altered grains display lower SiO₂ and ZrO₂ contents. Enrichment of Th and U in altered zircon preferentially involves coupled substitution (Ca²⁺ + (Th,U)⁴⁺ ↔ 2Zr⁴⁺ + 2Si⁴⁺), implying that significant U and Th may enter the Zr and Si position in zircon. Negative correlation of Zr vs. Hf and Al may indicate that Hf and Al have been introduced to the zircon during later fluid alteration rather than during the primary magmatic event. A two-stage metallogenetic model is proposed for the alteration processes and origin of U- and Th-bearing minerals in the Um Ara alkali-feldspar granite: 1) the first stage was dominated by hydrothermal alteration and accompanied by albitization, k-feldspathization, desilicification, chloritization, hematitization, silicification, argillization, fluoritization and corrosion of primary U-bearing minerals. Solid-solution between thorite and zircon occurred during this stage. The second stage occurred at the near-surface profile where circulating meteoric water played an important role in mobilizing the early formed primary U-bearing minerals. Uranium was likely transported as a calcium uranyl carbonate complexes. When these complexes lost their stabilities by precipitation of calcite, they decomposed in the presence of silica to form uranophane.     

Thermodynamic characterization of boltwoodite and uranophane: Enthalpy of formation and aqueous solubility

Boltwoodite and uranophane are uranyl silicates common in oxidized zones of uranium ore deposits. An understanding of processes that impact uranium transport in the environment, especially pertaining to the distribution of uranium between solid phases and aqueous solutions, ultimately requires determination of thermodynamic parameters for such crystalline materials. We measured formation enthalpies of synthetic boltwoodites, K(UO₂)(HSiO₄)·H₂O and Na(UO₂)(HSiO₄)·H₂O, and uranophane, Ca(UO₂)₂(HSiO₄)₂·5H₂O, by high temperature oxide melt solution calorimetry. We also studied the aqueous solubility of these phases from both saturated and undersaturated conditions at a variety of pH. The combined data permit the determination of standard enthalpies, entropies and Gibbs free energies of formation for each phase and analysis of its potential geological impact from a thermodynamic point of view.     

Effects of aqueous complexation on reductive precipitation of uranium by Shewanella putrefaciens

We have examined the effects of aqueous complexation on rates of dissimilatory reductive precipitation of uranium by Shewanella putrefaciens. Uranium(VI) was supplied as sole terminal electron acceptor to Shewanella putrefaciens (strain 200R) in defined laboratory media under strictly anaerobic conditions. Media were amended with different multidentate organic acids, and experiments were performed at different U(VI) and ligand concentrations. Organic acids used as complexing agents were oxalic, malonic, succinic, glutaric, adipic, pimelic, maleic, citric, and nitrilotriacetic acids, tiron, EDTA, and Aldrich humic acid. Reductive precipitation of U(VI), resulting in removal of insoluble amorphous UO₂ from solution, was measured as a function of time by determination of total dissolved U. Reductive precipitation was measured, rather than net U(VI) reduction to U(IV), to assess overall U removal rates from solution, which may be used to gauge the influence of chelation on microbial U mineralization. Initial linear rates of U reductive precipitation were found to correlate with stability constants of 1:1 aqueous U(VI):ligand and U(IV):ligand complexes. In the presence of strongly complexing ligands (e.g., NTA, Tiron, EDTA), UO₂ precipitation did not occur. Our results are consistent with ligand-retarded precipitation of UO₂, which is analogous to ligand-assisted solid phase dissolution but in reverse: ligand exchange with the U⁴⁺ aquo cation acts as a rate-limiting reaction moderating coordination of water molecules with U⁴⁺, which is a necessary step in UO₂ precipitation. Ligand exchange kinetics governing dissociation rates of ligands from U(VI)-organic complexes may also influence overall UO₂ production rates, although the magnitude of this effect is unclear relative to the effects of U(IV)-organic complexation. Our results indicate that natural microbial-aqueous systems containing abundant organic matter can inhibit the formation of biogenic amorphous UO₂.     

Uranophane dissolution and growth in CaCl2-SiO2(aq) test solutions

The dissolution and growth of uranophane [Ca(UO₂)₂(SiO₃OH)₂·5H₂O] have been examined in Ca- and Si-rich test solutions at low temperatures (20.5 ± 2.0 °C) and near-neutral pH (∼6.0). Uranium-bearing experimental solutions undersaturated and supersaturated with uranophane were prepared in matrices of ∼10⁻² M CaCl₂ and ∼10⁻³ M SiO₂(aq). The experimental solutions were reacted with synthetic uranophane and analyzed periodically over 10 weeks. Interpretation of the aqueous solution data permitted extraction of a solubility constant for the uranophane dissolution reaction and standard state Gibbs free energy of formation for uranophane ( kJ mol⁻¹).     

Alteration of uraninite from the Nopal I deposit,Pen˜a Blanca District,Chihuahua, Mexico,compared to degradation of spent nuclear fuel in the proposed U.S. high-level nuclear waste repository at Yucca Mountain,Nevada

At the Nopal I uranium deposit, primary uraninite (nominally UO_2+x) has altered almost completely to a suite of secondary uranyl minerals. The deposit is located in a Basin and Range horst composed of welded silicic tuff; uranium mineralization presently occurs in a chemically oxidizing and hydrologically unsaturated zone of the structural block. These characteristics are similar to those of the proposed U.S. high-level nuclear waste (HLW) repository at Yucca Mountain, Nevada. Petrographic analyses indicate that residual Nopal I uraninite is fine grained (5–10 μm) and has a low trace element content (average about 3 wt%). These characteristics compare well with spent nuclear fuel. The oxidation and formation of secondary minerals from the uraninite have occurred in an environment dominated by components common in host rocks of the Nopal I system (e.g. Si, Ca, K, Na and H₂O) and also common to Yucca Mountain. In contrast, secondary phases in most other uranium deposits form from elements largely absent from spent fuel and from the Yucca Mountain environment (e.g. Pb, P and V). The oxidation of Nopal I uraninite and the sequence of alteration products, their intergrowths and morphologies are remarkably similar to those observed in reported corrosion experiments using spent fuel and unirradiated UO₂ under conditions intended to approximate those anticipated for the proposed Yucca Mountain repository. The end products of these reported laboratory experiments and the natural alteration of Nopal I uraninite are dominated by uranophane [nominally Ca(UO₂)₂Si₂O₇·6H₂O] with lesser amounts of soddyite [nominally (UO₂)₂SiO₄·2H₂O] and other uranyl minerals. These similarities in reaction product occurrence developed despite the differences in time and physical—chemical environment between Yucca Mountain-approximate laboratory experiments and Yucca Mountain-approximate uraninite alteration at Nopal I, suggesting that the results may reasonably represent phases likely to form during long-term alteration of spent fuel in a Yucca Mountain repository. From this analogy, it may be concluded that the likely compositional ranges of dominant spent fuel alteration phases in the Yucca Mountain environment may be relatively limited and may be insensitive to small variations in system conditions.     

Experimental study of uraninite solubility in aqueous HCl solutions at 500°C and 1 kbar

Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)₄⁰, U(OH)₂Cl₂⁰, and UOH Cl₃⁰ Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO₂(aq), −1374.57 for U(OH)₂ Cl₂⁰, and −1265.49 for UOH Cl₃⁰, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO₂(cr) = UO₂(aq), pK ₀ = 6.64; UO₂(cr) + 2HCl⁰ = U(OH)₂ Cl₂⁰, pK ₂ = 3.56; and UO₂(cr) + 3HCl⁰ = UOHcl₃⁰ + H₂O, pK ₃ = 3.05. The value pK ₁ ≈ 5.0 was obtained as a first approximation for the equilibrium UO₂(cr) + H₂O + HCl⁰ = U(OH)₃Cl⁰. The constant of the reaction UO₂(cr) + 4HCl⁰ = UCl₄⁰ + 2H₂O (pK ₄ = 7.02) was calculated taking into account the ionization constants of U Cl₄⁰ and U(OH)₄⁰, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO_{2 + x} /UO₂ redox pair oxidized Au(cr) to Au⁺(aq), which was then reduced under the influence of stronger reducers.     

Heterogeneous Equilibria in Saturated Aqueous Solutions of Uranophane

Heterogeneous equilibria in the system Ca(HSiUO₆)₂ · 5H2O_(c)–aqueous solution were studied over broad ranges of pH, ionic strength, and ionic composition of the solution, and the pH range of stability of Ca uranyl silicate is determined. Hydrolysis products of Ca uranyl silicate are identified, and their solubility is determined. The equilibrium constant of the dissolution reaction and the standard Gibbs function of formation of Ca(HSiUO₆)₂ · 5H₂O are calculated from experimental data, and solubility curves of uranophane and equilibrium speciation diagrams for U(VI), Si(IV), and Ca(II) in coexisting aqueous solutions and solid phases are calculated.     

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO₂(CO₃)₃²⁻ and Ca₂UO₂(CO₃)₃⁰(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO₃ solutions equilibrated with either ambient air (430 ppm CO₂) or 2% CO₂ in the presence of 0, 1.8, or 8.9 mM Ca²⁺. Under conditions where the Ca₂UO₂(CO₃)₃⁰(aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca₂UO₂(CO₃)₃⁰(aq) accurately simulated the effect of Ca²⁺ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca²⁺ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.     

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH₃ to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. The objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al³⁺ (2.8 or 5 mM), HCO₃⁻ (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO₂(CO₃)₂⁻² and UO₂(CO₃)₃⁻⁴) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO₂(OH)₃⁻ and UO₂(OH)₄⁻²) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO₂CO₃], cejkaite [Na₄(UO2)(CO₃)₃] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO₂)(SiO₄)·1.5H₂O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.     

Eruptive history of the Barombi Mbo Maar, Cameroon Volcanic Line, Central Africa: Constraints from volcanic facies analysis

his study presents the first and detail field investigations of exposed deposits at proximal sections of the Barombi Mbo Maar (BMM), NE Mt Cameroon, with the aim of documenting its past activity, providing insight on the stratigraphic distribution, depositional process, and evolution of the eruptive sequences during its formation. Field evidence reveals that the BMM deposit is about 126m thick, of which about 20m is buried lowermost under the lake level and covered by vegetation. Based on variation in pyroclastic facies within the deposit, it can be divided into three main stratigraphic units: U₁, U₂ and U₃. Interpretation of these features indicates that U₁ consists of alternating lapilli-ash-lapilli beds series, in which fallout derived individual lapilli-rich beds are demarcated by surges deposits made up of thin, fine-grained and consolidated ash-beds that are well-defined, well-sorted and laterally continuous in outcrop scale. U₂, a pyroclastic fall-derived unit, shows crudely lenticular stratified scoriaceous layers, in which many fluidal and spindle bombs-rich lapilli-beds are separated by very thin, coarse-vesiculatedash-beds, overlain by a mantle xenolith- and accidental lithic-rich explosive breccia, and massive lapilli tuff and lapillistone. U3 displays a series of surges and pyroclastic fall layers. Emplacement processes were largely controlled by fallout deposition and turbulent diluted pyroclastic density currents under “dry” and “wet” conditions. The eruptive activity evolved in a series of initial phreatic eruptions, which gradually became phreatomagmatic, followed by a phreato-Strombolian and a violent phreatomagmatic fragmentation. A relatively long-time break, demonstrated by a paleosol between U₂ and U₃, would have permitted the feeding of the root zone or the prominent crater by the water that sustained the next eruptive episode, dominated by subsequent phreatomagmatic eruptions. These preliminary results require complementary studies, such as geochemistry, for a better understanding of the changes in the eruptive styles, and to develop more constraints on the maar’s polygenetic origin.     

Mineral Chemistry of Albite-Enriched Granitoids at Um Ara,Southeastern Desert,Egypt

Mineral chemistry and typomorphic characteristics are used to monitor the physicochemical evolution of late-magmatic to postmagmatic alteration processes that resulted in the development of a radioactive and albite-enriched microgranite stock. The mineral paragenesis indicates that postmagmatic fluids were enriched in Nb, Zn, Mn, U., Th, Zr, and Y, in addition to Rb, Li, and F Manganocolumbite with extremely high Nb/(Nb+Ta) (0.99), Mn/(Mn+Fe) (0.82), and zircon with high Zr/(Zr+Hf) (0.97) indicate crystallization under alkaline, relatively high-temperature conditions (>425° C). The close association of manganocolumbite, Nb-Mn-Zn- rich ilmenite (with 1.2 to 14.5 wt% ZnO), spessartine garnet (with 68.2-89.4 mol% spessartine), zircon, xenotime, zinnwaldite mica (up to 5.98 wt% F), and fluorite indicates the strong affinity of the elements of Nb, Y., Zr, Mn, and Zn for stable complexing by K⁺, Na⁺, Li⁺, and F^? rich supercritical fluids during the course of extraction and transportation.

The enrichment of the interacting fluid in U and Th is depicted by the presence of up to 1.6% UO₂ in manganocolumbite and Hf-bearing zircon, and up to 10.5% ThO₂ in monazite, in addition to locally abundant thorite and uranophane. It is suggested that the uranium mineralization, mainly as fracture fillings, formed during the waning stage of hydrothermal activity.     

Deposition of uraninite in microfissures of uranothorianite

Deposition of uraninite in microfissures of uranothorianite crystals, in a proluvialdeluvial placer of titaniferous magnetite (with Pb and many other impurities) is understandably the result of self-oxidation of U⁴⁺ to U⁶⁺ in the mineral (e.g. by radiogenic oxygen produced by decay of thorium in the presence of lead), its outward migration (as by leaching), and then its partial reduction, UO₃ to UO₂, deposition, and preservation, under certain conditions, as in the Arctic or Japan.     

Uranium co-precipitation with iron oxide minerals

In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals (such as hematite [α-Fe₂O₃] and goethite [α-FeOOH]) and occlusion of U(VI) by Fe-oxide coatings are processes that can retard U transport in environments. In aged U-contaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by coprecipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, Fe-oxide phases (containing 0.5 to 5.4 mol% U/(U + Fe)) were synthesized by means of solutions of U(VI) and Fe(III). Wet chemical (digestions and chemical extractions) and spectroscopic techniques were used to characterize the synthesized Fe oxide coprecipitates after rinsing in deionized water. Leaching the high mol% U solids with concentrated carbonate solution (for sorbed and solid-phase U(VI) species) typically removed most of the U, leaving, on average, about 0.6 mol% U. Oxalate leaching of solids with low mol% U contents (about 1 mol% U or less) indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol% U (∼4 wt% U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol% U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO₂²⁺ species (such as the IR asymmetric υ₃ stretch for O = U = O for uranyl). These spectral features were undetectable in carbonate- or oxalate-leached solids, suggesting solid phase and sorbed U(VI)O₂²⁺ species are extracted by the leach solutions. Uranium L₃-edge x-ray absorption spectroscopic (XAFS) analyses of the unleached U-Fe oxide solids with less than 1 mol% U reveal that U(VI) exists with four O atoms at radial distances of 2.19 and 2.36 Å and second shell Fe at a radial distance at 3.19 Å.Because of the large ionic radius of UO₂²⁺ (∼1.8 Å) relative to that of Fe³⁺ (0.65 Å), the UO₂²⁺ ion is unlikely to be incorporated in the place of Fe in Fe(III)-oxide structures. Solid-phase U(VI) can exist as the uranyl [U(VI)O₂²⁺] species with two axial U-O double bonds and four or more equatorial U-O bonds or as the uranate species (such as γ-UO₃) without axial U-O bonds. Our findings indicate U⁶⁺ (with ionic radii of 0.72 to 0.8 Å, depending on the coordination environment) is incorporated in the Fe oxides as uranate (without axial O atoms) until a point of saturation is reached. Beyond this excess in U concentration, precipitating U(VI) forms discrete crystalline uranyl phases that resemble the uranyl oxide hydrate schoepite [UO₂(OH)₂·2H₂O]. Molecular modeling studies reveal that U⁶⁺ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.     

In situ U–Pb dating of micro-baddeleyite by secondary ion mass spectrometry

We introduce a technique for U–Pb dating of baddeleyite using secondary ion mass spectrometry (SIMS) in situ analysis of ng-mass crystals that cannot be efficiently extracted by conventional mineral separation techniques. Average ²⁰⁷Pb/²⁰⁶Pb ages for Precambrian baddeleyite crystals are within < 0.3% of the respective isotope dilution thermal ionization mass spectrometry (ID-TIMS) ages. ²⁰⁶Pb/²³⁸U ratios are corrected for instrumental fractionation calibrated through linear regression in a Pb/U relative sensitivity vs. UO₂⁺/U⁺ calibration plot. Calibration is performed on separated baddeleyite crystals (～ 100–200 μm in maximum dimension) mounted in random crystallographic orientation. ²⁰⁶Pb/²³⁸U ages for baddeleyite from Duluth gabbro (FC4b) and Kovdor are accurate within 1–2% when averaging 15–30 individual spot analyses and relative sensitivities calibrated on Phalaborwa baddeleyite. The relative difference of ²⁰⁶Pb/²³⁸U between large crystals and micro-baddeleyite from FC4b is within ～ 1%. Comparison between silicate glass and baddeleyite, as well as replicate analysis of the same grains in different orientations relative to the incidence direction of the primary beam support previous evidence for bias in Pb/U sensitivity in baddeleyite due to variable crystal orientations. We successfully utilized oxygen flooding and a UO₂⁺/U⁺-based calibration to significantly reduce orientation dependent bias.     

The effects of uranium speciation on the rate of U(VI) reduction by Shewanella oneidensis MR-1

We measured the kinetics of U(VI) reduction by Shewanella oneidensis MR-1 under anaerobic conditions in the presence of variable concentrations of either EDTA or dissolved Ca. We measured both total dissolved U and U(VI) concentrations in solution as a function of time. In separate experiments, we also measured the extent of U(VI) adsorption onto S. oneidensis in order to quantify the thermodynamic stabilities of the important U(VI)-bacterial surface complexes. In the EDTA experiments, the rate of U(IV) production increased with increasing EDTA concentration. However, the total dissolved U concentrations remained constant and identical to the initial U concentrations during the course of the experiments for all EDTA-bearing systems. Additionally, the U(VI) reduction rate in the EDTA experiments exhibited a strong correlation to the concentration of the aqueous U⁴⁺-EDTA complex. We conclude that the U(VI) reduction rate increases with increasing EDTA concentration, likely due to U⁴⁺-EDTA aqueous complexation which removes U(IV) from the cell surface and prevents UO₂ precipitation.In the Ca experiments, the U(VI) reduction rate decreased as Ca concentration increased. Our thermodynamic modeling results based on the U(VI) adsorption data demonstrate that U(VI) was adsorbed onto the bacterial surface in the form of a Ca-uranyl-carbonate complex in addition to a number of other Ca-free uranyl complexes. The observed U(VI) reduction rates in the presence of Ca exhibit a strong negative correlation to the concentration of the Ca-uranyl-carbonate bacterial surface complex, but a strong positive correlation to the total concentration of all the other Ca-free uranyl surface complexes. Thus, the concentration of these Ca-free uranyl surface complexes appears to control the rate of U(VI) reduction by S. oneidensis in the presence of dissolved Ca. Our results demonstrate that U speciation, both of U(VI) before reduction and of U(IV) after reduction, affects the reduction kinetics, and that thermodynamic modeling of the U speciation may be useful in the prediction of reduction kinetics in realistic geologic settings.     

Effects of seawater carbonate ion concentration and temperature on shell U, Mg, and Sr in cultured planktonic foraminifera

We investigate the sensitivity of U/Ca, Mg/Ca, and Sr/Ca to changes in seawater [CO₃²⁻] and temperature in calcite produced by the two planktonic foraminifera species, Orbulina universa and Globigerina bulloides, in laboratory culture experiments. Our results demonstrate that at constant temperature, U/Ca in O. universa decreases by 25 ± 7% per 100 μmol [CO₃²⁻] kg⁻¹, as seawater [CO₃²⁻] increases from 110 to 470 μmol kg⁻¹. Results from G. bulloides suggest a similar relationship, but U/Ca is consistently offset by ∼+40% at the same environmental [CO₃²⁻]. In O. universa, U/Ca is insensitive to temperature between 15°C and 25°C. Applying the O. universa relationship to three U/Ca records from a related species, Globigerinoides sacculifer, we estimate that Caribbean and tropical Atlantic [CO₃²⁻] was 110 ± 70 μmol kg⁻¹ and 80 ± 40 μmol kg⁻¹ higher, respectively, during the last glacial period relative to the Holocene. This result is consistent with estimates of the glacial-interglacial change in surface water [CO₃²⁻] based on both modeling and on boron isotope pH estimates. In settings where the addition of U by diagenetic processes is not a factor, down-core records of foraminiferal U/Ca have potential to provide information about changes in the ocean’s carbonate concentration.Below ambient pH (pH < 8.2), Mg/Ca decreased by 7 ± 5% (O. universa) to 16 ± 6% (G. bulloides) per 0.1 unit increase in pH. Above ambient pH, the change in Mg/Ca was not significant for either species. This result suggests that Mg/Ca-based paleotemperature estimates for the Quaternary, during which surface-ocean pH has been at or above modern levels, have not been biased by variations in surface-water pH. Sr/Ca increased linearly by 1.6 ± 0.4% per 0.1 unit increase in pH. Shell Mg/Ca increased exponentially with temperature in O. universa, where Mg/Ca = 0.85 exp (0.096*T), whereas the change in Sr/Ca with temperature was within the reproducibility of replicate measurements.