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1.
《Applied Geochemistry》1997,12(5):549-565
The Cigar Lake unconformity-type U deposit is one of the largest and highest grade U deposits in the Proterozoic Athabasca Basin, northern Saskatchewan, Canada. Cigar Lake has recently been the focus of an international, 3-a, collaborative program in which this U deposit was studied as a natural analogue for a spent nuclear fuel repository. The deposit is located near the eastern margin of the Athabasca Basin, 430 m below the surface, at the intersection between Hudsonian-age faults and the unconformity between Athabasca group sandstones and Aphebian metasediments. Three stages of U mineralization have been identified based on cross-cutting relationships and textures observed in thin section and back-scattered electron (BSE) images, O isotope data and chemical compositions. All stages of U mineralization have been variably altered to Ca-rich, U-hydrate minerals or uranyl oxide hydrate minerals and coffinite.UPb chemical ages of the 3 stages of U mineralization from Cigar Lake coincide with the 3 major fluid events that precipitated clay and silicate minerals at 1500 Ma, 950 Ma, and 300 Ma, throughout the entire Athabasca Basin. Stage 1 and 2 uraninite and pitchblende have the lowest δ18O values that range from −30.1 ‰ to −15.2‰; whereas, stage 3 uraninite has δ18O values ranging from −10.0‰ to −3.4‰. Uranyl oxide hydrate minerals have δ18O values that range from −11.3‰ to −8.2‰; whereas, uranyl minerals have much higher δ18O values. Based on UPb chemical ages,δ18O values, and petrographic relationships of U alteration minerals associated with primary U mineralization, the Cigar Lake U ore is similar to U ore from other unconformity-type U deposits in the Athabasca Basin. Therefore, the Cigar Lake ore deposit, although surrounded by clay and sandstone barriers, has been effected by the same fluid events that have altered other unconformity-type U deposits in the Athabasca Basin.The 3 stages of ore formation and associated alteration minerals permit the detailed study of fluids responsible for U deposition and alteration. This information provides the necessary context for the evaluation of the Cigar Lake deposit as a “natural analogue” for the disposal of spent nuclear fuel in underground vaults in rocks of the Canadian Shield.  相似文献   

2.
The surface reactivity of biogenic, nanoparticulate UO2 with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO2. Synthesis of biogenic UO2 was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO2 as a function of particle size and surface-associated organic matter. The N2-BET surface areas of the two biogenic UO2 samples following the washing procedures are 128.63 m2 g−1 (NAUO2) and 92.56 m2 g−1 (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO2 (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U LIII-edge EXAFS spectra for biogenic UO2 (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO2. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO2 is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m−2 UO2 (bulk uraninite), 2.34 ± 0.12 μmol m−2 UO2 (NAUO2), and 2.57 ± 0.10 μmol m−2 UO2 (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO2 indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)6 sorbs as bidentate, edge-sharing complexes to UO8 polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO2 surface. Surface-associated organic matter on the biogenic UO2 particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO2 surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.  相似文献   

3.
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.  相似文献   

4.
《Applied Geochemistry》1994,9(6):713-732
At the Nopal I uranium deposit, primary uraninite (nominally UO2+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.  相似文献   

5.
An alkaline brine containing uranyl (UO22+) leaked to the thick unsaturated zone at the Hanford Site. We examined samples from this zone at microscopic scale to determine the mode of uranium occurrence—microprecipitates of uranyl (UO22+) silicate within lithic-clast microfractures—and constructed a conceptual model for its emplacement, which we tested using a model of reactive diffusion at that scale. The study was driven by the need to understand the heterogeneous distribution of uranium and the chemical processes that controlled it. X-ray and electron microprobe imaging showed that the uranium was associated with a minority of clasts, specifically granitic clasts occupying less than four percent of the sediment volume. XANES analysis at micron resolution showed the uranium to be hexavalent. The uranium was precipitated in microfractures as radiating clusters of uranyl silicates, and sorbed uranium was not observed on other surfaces. Compositional determinations of the 1-3 μm precipitates were difficult, but indicated a uranyl silicate. These observations suggested that uranyl was removed from pore waters by diffusion and precipitation in microfractures, where dissolved silica within the granite-equilibrated solution would cause supersaturation with respect to sodium boltwoodite. This hypothesis was tested using a reactive diffusion model operating at microscale. Conditions favoring precipitation were simulated to be transient, and driven by the compositional contrast between pore and fracture space. Pore-space conditions, including alkaline pH, were eventually imposed on the microfracture environment. However, conditions favoring precipitation were prolonged within the microfracture by reaction at the silicate mineral surface to buffer pH in a solubility limiting acidic state, and to replenish dissolved silica. During this time, uranyl was additionally removed to the fracture space by diffusion from pore space. Uranyl is effectively immobilized within the microfracture environment within the presently unsaturated Vadose Zone.  相似文献   

6.
贵州云峰铝土矿中铀矿物的发现   总被引：1，自引：1，他引：0  
有关铝土矿中铀富集的报道很多,但至今未见独立铀矿物存在的相关文献。本次研究采用岩相学观察、X衍射(XRD)、ICP-MS、电子探针(EPMA)、拉曼光谱分析等手段,对黔中典型的铝土矿——云峰铝土矿中的晶质铀矿进行了研究。研究发现该铝土矿床中,铀富集明显(w(U)(18×10~(-6)～62×10~(-6)),平均值35×10~(-6)),铀矿物大小呈微米至亚微米级,围绕锐钛矿边缘生长、或充填于高岭石微裂隙中、或散布于与黄铁矿密切相关的高岭石或硬水铝石中。铀矿物的主要组分为UO_2(w(UO_2)为52.2%～80.88%)和TiO_2(w(TiO_2)为1.85%～14.98%);电子探针面扫描显示铀矿物中钛分布不均匀;铀矿物的拉曼特征波长为442 cm~(-1)和454 cm~(-1),因此,初步推测铀矿物为晶质铀矿和含钛晶质铀矿。其形成过程大致如下,来源于下寒武统牛蹄塘组黑色岩系中的铀(U~(4+))在风化过程中氧化为U~(6+)、析出、被Al~-, Fe~-氧化物/氢氧化物吸附;在沉积和成岩过程中,随着三水铝石转变为勃姆石和硬水铝石、铁氧化/氢氧化物转变为黄铁矿,吸附的铀解吸、还原(U~(6+)至U~(4+))、最后形成铀矿物。  相似文献   

7.
The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere complexes at sites that do not react chemically with carbonate ions. Uranyl is bound by singly-coordinated surface groups present at particular edges of Fe-octahedra of ferrihydrite while another set of singly-coordinated surface groups may form double-corner bidentate complexes with carbonate ions. The uranyl surface speciation strongly changes in the presence of carbonate due to the specific adsorption of carbonate ions as well as the formation of ternary uranyl-carbonate surface complexes. Data analysis with the CD model suggests that a uranyl tris-carbonato surface complex, i.e. (UO2)(CO3)34−, is formed. This species is most abundant in systems with a high pH and carbonate concentration. This finding differs significantly from previous interpretations made in the literature. At high pH and low carbonate concentrations, as can be prepared in CO2-closed systems, the model suggests the additional presence of a ternary uranyl-monocarbonato complex. The binding mode (type A or type B complex) is uncertain. At high uranyl concentrations, uranyl polymerizes at the surface of ferrihydrite giving, for instance, tris-uranyl surface complexes with and without carbonate. The similarities and differences between U(VI) adsorption by goethite and ferrihydrite are discussed from a surface structural point of view.  相似文献   

8.
X-ray diffraction (XRD) studies on the radioactive ore samples from various parts of Rajasthan and Haryana have revealed the presence of several uranium and other atomic mineral occurrences in the albitite belt of western India. The primary uranium minerals (PUMs) are uraninite and brannerite, whereas, the secondary uranium minerals (SUMs) show considerable speciations: phosphate, silicate, hydrous oxide hydrate, and vanadate. Multiple oxides (MOs) are davidite, fergusonite, aeschynite-(Y), microlite, samarskite, euxenite, betafite, and columbite-tantalite. The thorium minerals are huttonite, thorite, uranoan-thorite, thorianite, thorutite, and brabantite. The yttrium and REE-bearing minerals are xenotime, britholite, allanite, chevkinite, tritomite, and monazite. It is noted that the measured unit cell dimension (a0) of the investigated uraninites ranges from 5.4110 Å to 5.4646 Å. The highest unit cell dimension (5.4646 Å) represents a composition (or oxidation grade) of UO2.05, whereas, the lowest one (5.4110 Å) corresponds to a composition of UO2.54. Furthermore, it is also apparent that, with increase in oxidation grade, there is a concomitant decrease in unit cell dimension. As most of the values of ao of uraninites from the albitite belt are high (> 5.45 Å), it may be inferred that the overall temperature of formation of uraninites of the albitite belt was higher (ca. 400°C). However, the low values of a0 in certain localities could be due to the prevalence of relatively low and fluctuating temperature regimes locally (ca. 400°–100° C). Numerous occurrences of refractory, multiple oxides, and REE minerals, in association with uranium mineralisation, also support a high-temperature origin for the investigated uraninites. Binary data plots of unit cell dimension (a0) versus oxidation grade/composition (UO2+x) of uraninites (n = 36) suggest that the gross uranium mineralisation in the albitite belt of western India is mainly linked to regional metamorphism, anatexis, granitic intrusion, metasomatism, and contact metamorphosed granite-pegmatite aureoles and granite-related vein type with hydrothermal overprints, including redistribution of intrinsic sedimentary uranium and its concentration along suitable structural locales. These interpretations are consistent with the known gross geologic features of the albitite belt. Furthermore, the presence of marialite (calcian) in many places in the albitite belt also supports such a contention, as this mineral is known to be restricted to metamorphic and metasomatic environments. The speciation of secondary uranium minerals could be due to the higher oxidation of U4+ to U6+ in surface to near-surface conditions and its (U6+) remobilisation as uranyl ions. The combination of moving uranyl ions with available cations and anions en route caused re-precipitation of U as diversified assemblages of low-temperature uranyl minerals under suitable physicochemical conditions.  相似文献   

9.
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.
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.

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

With 3 Figures  相似文献   

10.
We present a rapid and accurate technique for making in situ U-Pb isotopic measurements of uranium oxide minerals that utilizes both electron and ion microprobes. U and Pb concentrations are determined using an electron microprobe, whereas the isotopic composition of Pb for the same area is measured using a high-resolution ion microprobe. The advantages of this approach are: mineral separation and chemical digestion are unnecessary; homogenous uranium oxide standards, which are difficult to obtain, are not required; and precise and accurate U-Pb ages on ～10 μm spots can be obtained in a matter of hours. We have applied our method to study the distribution of U-Pb ages in complexly intergrown uranium oxides from the unconformity-type Cigar Lake uranium deposit, Saskatchewan, Canada. In situ U-Pb results from early formed uraninite define a well-correlated array on concordia with upper and lower intercepts of 1467 ± 63 Ma and 443 ± 96 Ma (±lσ), respectively. The 1467 Ma age is interpreted as the minimum age of mineralization and is consistent with the age of clay-mineral alteration (～1477 Ma) and magnetization of diagenetic hematite (1650 to 1450 Ma) that is associated with these unconformity-type uranium deposits and early diagenesis of the Athabasca Basin sediments. In situ U-Pb isotopic analyses of uraninite and coffinite can document the Pb?/U heterogeneities that can occur on a scale of 15 to 30 μm, thus providing relatively accurate information regarding the timing of fluid interactions associated with the evolution of these deposits.  相似文献   

11.
The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of ∼10−8 M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO2.0 to UO2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO2.25 (U4O9) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested conditions. Although U(V) has been observed in electrochemical studies on the dissolution of spent nuclear fuel, this is the first investigation that demonstrates the formation of a stable U(V) intermediate phase on the surface of submicron-sized uraninite particles suspended in aqueous solutions.  相似文献   

12.
Uraninite solubility in HF solutions (0.0001–0.5 m) was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the predominant U(IV) species in aqueous solution are U(OH)40, U(OH)3F0, and U(OH)2 F20. Using the results of uraninite solubility measurement, the Gibbs free energies of the uranium (IV) species were calculated at 500°C and 1000 bar (kJ/mol): −986.55 for UO2(aq), −1712.42 for U(OH)3F0, −1755.53 for U(OH)2F20, and the equilibrium constants of the uraninite solubility in water and HF solutions were estimated: UO2(κ) = UO2(aq), which is similar to UO2(cr) + 2H2O = U(OH)40, pK0 = 6.64; UO2(cr) + HF0 + H2O = U(OH)3F0, K1 = 0.0513; UO2(cr) + 2HF0 = U(OH)2F20K2 = 7.00 × 10−4. Approximate values K3 = 5.75 × 10−3 and K4 = 6.7 × 10−2 were obtained for equilibria UO2(cr) + 4HF0 =UF40 + 2H2O and UO2(cr) + 4HF = UF40 + 2H2O. Maximum observed in the uranium concentration curve as a function of HF concentration can be explained by the decrease (to < 1) of activity coefficient ratio of HF0 to U(OH)3F0 with increasing HF concentrations.  相似文献   

13.
The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O2 and 0.0017% CO2) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO2 was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO2 occurred in preference to precipitation of UO3·2H2O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).  相似文献   

14.
The importance of geochronology in the study of mineral deposits in general, and of unconformity-type uranium deposits in particular, resides in the possibility to situate the critical ore-related processes in the context of the evolution of the physical and chemical conditions in the studied area. The present paper gives the results of laser step heating 40Ar/39Ar dating of metamorphic host-rock minerals, pre-ore and syn-ore alteration clay minerals, and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) U/Pb dating of uraninite from a number of basement- and sediment-hosted unconformity-related deposits in the Athabasca Basin, Canada. Post-peak metamorphic cooling during the Trans-Hudson Orogen of rocks from the basement occurred at ca 1,750 Ma and gives a maximum age for the formation of the overlying Athabasca Basin. Pre-ore alteration occurred simultaneously in both basement- and sandstone-hosted mineralizations at ca 1,675 Ma, as indicated by the 40Ar/39Ar dating of pre-ore alteration illite and chlorite. The uranium mineralization age is ca 1,590 Ma, given by LA-ICP-MS U/Pb dating of uraninite and 40Ar/39Ar dating of syn-ore illite, and is the same throughout the basin and in both basement- and sandstone-hosted deposits. The mineralization event, older than previously proposed, as well as several fluid circulation events that subsequently affected all minerals studied probably correspond to far-field, continent-wide tectonic events such as the metamorphic events in Wyoming and the Mazatzal Orogeny (ca 1.6 to 1.5 Ga), the Berthoud Orogeny (ca 1.4 Ga), the emplacement of the McKenzie mafic dyke swarms (ca 1.27 Ga), the Grenville Orogeny (ca 1.15 to 1 Ga), and the assemblage and break-up of Rodinia (ca 1 to 0.85 Ga). The results of the present work underline the importance of basin evolution between ca 1.75 Ga (basin formation) and ca 1.59 Ga (ore deposition) for understanding the conditions necessary for the formation of unconformity-type uranium deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

15.
An attempt has been made in Chinnar sub basin of Dharmapuri district, South India to isolate the geochemistry of uranium occurrences in groundwater. The geology of the area is mainly of charnockite and granite gneiss. Groundwater samples were collected for two different seasons post and pre monsoon in two different litho units (granite gneiss and charnockite) and analysed for major, minor and uranium concentrations. Higher uranium (18.45 μg L?1) has been recorded during pre monsoon season in granite gneiss with increasing pH. The saturation index calculation for the groundwater isolated minerals like uaraninite, coffinite, haiweeite and soddyite to be precipitating and uranium oxides like UO2.25, UO2.25beta, UO2.33beta as oversaturated. The Eh-pH diagram attempted represents solubility of uraninite within the pH range of 6.0 to 8.0. The study isolate uranium in groundwater of the study area is controlled by the presence of (U4O9) uranium oxide.  相似文献   

16.
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.  相似文献   

17.
The computer program PHREEQC was used to determined the distribution, chemical speciation and mineral saturation indices in a fresh groundwater environment with limited mining activities in the adjoining areas. The aim was mainly to determine the potential risk of a coastal plain aquifer contamination by some potentially toxic elements. The results show that the elements Ba, Cd, Cu, Fe, Mn, Ni, Rb, Sr, and Zn are distributed as free metal ions. Arsenic is in the neutral form of H3AsO3 o, while three species of aluminium [Al3+, AlOH2, Al(OH)2 +] dominate. The major species of uranium include UO2CO3, UO22++, UO2+, and UO2OH+, respectively, in order of abundance. The groundwater is saturated with respect to alunite [KAl3 (SO4)2 (OH)6], basaluminite [Al4 (OH)10 SO4], boehmite [Al(OH)], Cu metal (Cu), cuprous ferrite (CuFeO2), diaspore [AlO(OH)], gibbsite [Al(OH)3], goethite (FeOOH), hematite (Fe2O3), magnetite (Fe3O4) and uraninite (UO2). Most of the species are not mobile under the prevailing pH (3.3 to 5.9) and Eh (7 to 158 mV) conditions. The mobile ones are very low in concentration and will be immobilized by precipitation of mineral phases. The study concludes that presently these species do not pose any risk to the aquifer.  相似文献   

18.
Uranium minerals from the San Marcos District, Chihuahua, Mexico   总被引：1，自引：0，他引：1  
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 (UO2+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.  相似文献   

19.
The concentrations of uranium, iron and the major constituents were determined in groundwater samples from aquifer containing uranyl phosphate minerals (meta-autunite, meta-torbernite and torbernite) in the Köprüba?? area. Groundwater samples from wells located at shallow depths (0.5–6 m) show usually near neutral pH values (6.2–7.1) and oxidizing conditions (Eh = 119–275 mV). Electrical conductivity (EC) values of samples are between 87 and 329 μS/cm?1. They are mostly characterized by mixed cationic Ca dominating bicarbonate types. The main hydrogeochemical process is weathering of the silicates in the shallow groundwater system. All groundwater in the study area are considered undersaturated with respect to torbernite and autunite. PHREEQC predicted UO2(HPO4) 2 2? as the unique species. The excellent positive correlation coefficient (r = 0.99) between U and PO4 indicates the dissolved uranium in groundwater would be associated with the dissolution of uranyl phosphate minerals. The groundwater show U content in the range 1.71–70.45 μg/l but they are mostly lower than US EPA (2003) maximum contaminant level of 30 μg/l. This low U concentrations in oxic groundwater samples is attributed to the low solubility of U(VI) phosphate minerals under near neutral pH and low bicarbonate conditions. Iron closely associated with studied sediments, were also detected in groundwater. The maximum concentration of Fe in groundwater samples was 2837 μg/l, while the drinking water guidelines of Turkish (TSE 1997) and US EPA (2003) were suggested 200 and 300 μg/l, respectively. Furthermore, iron and uranium showed a significant correlation to each other with a correlation coefficient (r) of 0.94. This high correlation is probably related to the iron-rich sediments which contain also significant amounts of uranium mineralization. In addition to pH and bicarbonate controlling dissolution of uranyl phosphates, association of uranyl phosphates with iron (hydr) oxides seems to play important role in the amount of dissolved U in shallow groundwater.  相似文献   

20.
Summary The crystal structure of liebigite, previously only incompletely known from a short note, has been determined from X-ray 4-circle diffractometer data and refined toR=0.030 for 3005 observed reflections. Liebigite from Joachimsthal, Böhmen, was used. It was found to crystallize in the polar orthorhombic space groupBba2–C 2v 17 witha=16.699(3),b=17.557(3),c=13.697(3) Å,V=4016 Å3 and a cell content of 8 Ca2UO2(CO3)3·11H2O. The structure contains UO2(CO3)3 units which are linked by two kinds of CaO4(H2O)4 polyhedra and one kind of CaO3(H2O)4 polyhedron to form puckered Ca2UO2(CO3)3·8H2O layers parallel to (010). These layers are interconnected only by hydrogen bonds, both directly as well as via three additional interlayer H2O molecules, two of which show positional disorder.
Die Kristallstruktur des Liebigits, Ca2UO2(CO3)3·11H2O
Zusammenfassung Die Kristallstruktur des Minerals Liebigit, die bis jetzt nur unzureichend bekannt war, wurde mit Röntgen-Vierkreisdiffraktometer-Daten bestimmt und für 3005 beobachtete Reflexe aufR=0,030 verfeinert. Der untersuchte, von Joachimsthal, Böhmen, stammende Liebigit kristallisiert in der polaren rhombischen RaumgruppeBba2–C 2v 17 mita=16,699(3),b=17,557(3),c=13,697(3) Å,V=4016 Å3 und einem Zellinhalt von 8 Ca2UO2(CO3)3·11H2O. Die Struktur enthält UO2(CO3)3-Gruppen, die durch zwei Arten von CaO4(H2O)4-Polyedern und eine Art von CaO3(H2O)4-Polyedern zu buckeligen Ca2UO2(CO3)3·8H2O-Schichten parallel (010) verknüpft sind. Diese Schichten sind nur durch Wasserstoffbrücken verbunden, und zwar sowohl direkt als auch mittels dreier zusätzlicher freier Wassermoleküle, von denen zwei eine Lagenfehlordnung aufweisen.

With 3 Figures  相似文献   

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