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Adsorption is believed to be a dominant mechanism of uranium distribution between solid and solution, and thus, to play a major role in uranium transport. Because iron oxides and hydroxides are abundant at the Earth's surface and are great adsorbents of uranium, we have examined natural rocks that contain iron minerals along with uranium, and also carried out Fe-U coprecipitation and aging experiments to find how uranium is distributed between Fe minerals. Transmission and scanning electron microscopy reveals that microcrystals (10-50 nm) of metatorbernite (Cu(UO2)2(PO4)28H2O) are scattered within nodules consisting of fine-grained (2-50 nm) goethite and hematite, where the ground water is undersaturated with respect to metatorbernite, for the natural rocks from the Koongarra ore deposit, Australia. The microscopy also reveals that microcrystals (a few nm) of dehydrated schoepite ((UO2)O0.25(OH)1.5) are formed among fine-grained hematite after aging coprecipitated Fe-U in the laboratory, and the solution is undersaturated with respect to schoepite. The beam size of microscopes is found to be important for the chemical analysis of such microcrystals. We detect a strong signal of uranium for a beam size < 40 nm; whereas a weak uranium signal is obtained for a beam size > 150 nm. Our results indicate that such a weak uranium signal should not be taken as a result of homogeneously distributed uranium over goethite and hematite surfaces by, for instance, adsorption. The micrcrystallization observed in both the field and laboratory suggests that fine grained uranyl minerals play a major role in uranium transport and migration.
Rock samples in the secondary ore deposit at Koongarra, Australia, were examined mineralogically to clarify the formation mechanism of saléeite (Mg(UO2)2(PO4)2.10H2O), a major secondary uranium mineral in the secondary ore deposit. Sklodowskite (MgSi2U2O11.7H2O) veinlets, present upstream of the ore deposit, are partially replaced by saléeite. Most grains of apatite (Ca5(P04)3F), an accessory mineral of the host rock, are also replaced by saléeite. Thermodynamic calculations by EQ3NR showed that the present Koongarra ground waters are undersaturated with respect to saléeite and also suggested that saléeite can be precipitated under the condition of higher U or P concentrations. Such conditions can be created at the reaction interfaces of dissolving sklodowskite, which releases U, or dissolving apatite, which releases P. The present study indicates that saléeite is formed by local microscale saturation upstream of the secondary ore deposit, which is different from the formation mechanism of saléeite downstream of the ore deposit, where saléeite microcrystals of 1 – 20 nm in size form by catalysis on iron minerals, the weathering products of the host rock.
A modelling study has been completed to understand the effect of rock alteration on uranium migration at the Koongarra ore deposit, Australia. The model considers the weathering process, the mechanism and rate of chlorite alteration, a major mineral of the host rock, and assumes the presence of reversible sorption sites of chlorite and the presence of reversible and irreversible sorption sites of the weathering products. One- and two-dimensional, calculated uranium concentrations were compared with those observed. Good agreement between the calculated and observed uranium concentration profiles was obtained only when an appropriate fraction of uranium is fixed to the irreversible sorption sites of Fe-minerals produced during weathering of chlorite. On the other hand, the conventional Kd model failed to estimate an adequate uranium concentration profile. The results suggest that the fixation of uranium to Fe-minerals has dominated the migration of uranium in the vicinity of the Koongarra ore deposit.
A rock specimen, collected downstream of the Koongarra uranium ore deposit, Australia, was examined mainly by high resolution transmission electron microscopy in order to understand the uranium fixation mechanism. Uranium was found to exist as saleeite (Mg(UO2)2(PO4)2.10H2O) microcrystals of 1 – 20 nm scattered between iron minerals (mainly goethite and hematite) of 2 – 50 nm. The microtextural relationship between saléeite and the iron minerals revealed that the iron minerals function as catalyst for the formation of saléeite. The intermediate metamict microstructures of the saléeite microcrystals are consistent with the estimated formation age of saléeite, 1 to 3 × 106 years. Uranium has been, thus, fixed as saléeite downstream as well as in the secondary ore deposit. Saléeite in the secondary ore deposit showed completely periodic to fully metamict microstructures, suggesting that saléeite, a major uranium mineral in the secondary ore deposit, probably began to form a few million years ago and continued to form for the next million years.
A series of hydrothermal experiments was performed to determine the effect of layer charge of starting materials on the smectite to illite reaction rate that might be applied to nuclear-waste repository design. The experiments were conducted on K-saturated <2μm fractions of Wyoming smectite (SWy-1) and Tsukinuno smectite (SKu-F, commercially, Kunipia-F) in a closed system at temperatures of 95, 150, 200, 250, 300°C for run durations of up to 477 days with a 1:20 mass ratio of solid to deionized water. The mean layer charge and tetrahedral charge of SKu-F are larger than those of SWy-1. The proportion of smectite layers in illite/smectite interstratified minerals rapidly decreases, and then slowly decreases with increase in reaction time; a plot of In (100/% smectite) vs. time produces two distinct straight lines in all experiments. These lines are suggestive of two first-order kinetic processes with different rates for this reaction; the first process has a greater rate than the second one. An Arrhenius plot of the reaction rates for each process produces a folding and straight lines for the first and second processes, respectively, suggesting that there are at least two parallel processes in the first process, and a dominant process is different between high- and low-temperature reactions. The activation energies of the first and second processes determined from the plots are the same for the two starting materials, meaning that the reaction mechanisms for the two starting materials are the same. However, the rate of the first process is different between the two starting materials, although that of the second process is similar. The difference in the rate of the first process results possibly from the difference in the amount of layer charge between the two starting smectites.
In order to clarify the effect of mineral alteration on nuclide migration, we examined the processes, mechanisms, and kinetics of chlorite weathering, and the uranium concentrations in minerals and rocks at Koongarra, Australia. The observed concentrations of uranium in rocks were compared to those calculated. The sequence of chlorite weathering may be simply expressed as a chlorite → vermiculite → kaolinite conversion. These minerals occur as a function of depth, which corresponds well to uranium concentrations on the meter scale. Iron minerals, closely related to the uranium redistribution, are released during the weathering. The first-order kinetic model of the weathering process suggests that the weathering rate is not constant but time-dependent. The uranium concentrations are qualitatively proportional to the extent of the weathering; the weathered part having higher uranium concentration. Uranium mainly occurs with iron minerals, and sub micron sized saléeite, a uranyl phosphate, is one of the most probable uranyl phases associated with the iron minerals. The uranium fixation mechanisms are probably saléeite microcrystal coprecipitation and sorption to the iron minerals. Our model, which describes uranium concentrations in rocks as a function of time, shows that the transition zone (a vermiculite dominant area) plays an important role in the uranium migration. We have established that weathering of chlorite has affected the redistribution of uranium for more than one million years. The present study demonstrates the significance of mineral alteration when we estimate nuclide migration for geologic time.
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