The weathering of chlorite, one of the major minerals of the host rock in the uranium ore deposit at Koongarra, Australia, was examined by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), electron microprobe analysis, and transmission electron microscopy (TEM). The conversion sequence of chlorite weathering is: (1) chlorite; (2) chlorite/vermiculite intergrade (showing XRD responses to various treatments intermediate between those of chlorite and vermiculite); (3) interstratified chlorite and vermiculite; (4) vermiculite; and (5) kaolinite. This sequence may be more simply expressed as chlorite ⤒ vermiculite ⤒ kaolinite. The weathering finally changed chlorite into sub-micrometer to micrometer sized Fe minerals and kaolinite. The transformation of chlorite to vermiculite is chemically characterized by an Fe and Mg loss with a slight decrease in the Al/Si ratio. Mg continues to be released throughout the weathering. Fe minerals formed through chlorite weathering are located between chlorite and vermiculite domains (a few μm in size) at first, and then accumulated between grain boundaries, occasionally forming veins. The distribution of Fe minerals is suggestive of preferential pathways of water movement. The time-dependent nature of mineral alteration demonstrated in the present study must be taken into account for the quantitative estimation of radionuclide migration.

We report the extremely high and selective uptake of selenium oxyanions by a novel anion exchanger, Ni1-xZn2x(OH)2(OCOCH3)2xnH2O (0.15<x<0.25). The tested Ni–Zn basic salt (x=0.24) exhibited very high selectivity for Se(IV) [Kd = 9.0 × 104 cm3/g with an initial Se(IV) concentration of 1 × 10-4 M] in the presence of 0.1 M C1− solution. The uptake of Se(IV) on the Ni–Zn basic salt was irreversible when treated with solutions containing 1 N C1− 1N NO3− or 1 N PO43−This novel exchanger also showed high Kd (2.6 × 103 cm3/g) for Se(VI), and therefore it is expected to be useful for decontamination and removal of selenium oxyanions from contaminated water.

The lichen Trapelia involuta from uraniferous spoil heaps in Cornwall, England, growing directly on the secondary uranium minerals, metazeunerite and metatorbernite, was examined by field-emission scanning electron microscopy and transmission electron microscopy to assess the effect of Trapelia on uranium migration. We observed metazeunerite, sericite and scorodite as well as unidentified Fe-, Pb/As-, Fe/As-, Al/P-, Pb-bearing minerals concentrated in the lichen exciple and medulla. In addition, metazeunerite also occurred in the epithecium. The chemistries, sizes, and occurrences of the above minerals in the lichen suggest that fixation of U as well as Pb, As, Fe, and Al is dependent on lichen physiological processes. We suggest Trapelia accumulates these elements from groundwater and precipitates the above minerals within specific tissues. Our results indicate that some lichens retard uranium migration by accumulating uranium from groundwater and forming uranium-bearing minerals within their tissues.

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.

The migration of radionuclides through rocks is one of the important paths to estimate the impact of radioactive waste disposal on the environment. Because some amount of the radionuclides is sorbed on the minerals of rocks during the migration, Kd model is considered to be used to estimate the radionuclide migration. However, long-term applicability of Kd model is not known.

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.

The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca2+ (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (Kd) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite Kd increased below pH 5 due to “specific sorption” of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca2+ in solution, an effect most pronounced at pH <5. These results show that Ca2+ limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca2+ was solubilized to depress neptunium sorption. This investigation demonstrates that Ca2+ contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium.

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.

A modelling study has been carried out to understand the effect of rock alteration on the fractionation of uranium among coexisting minerals (chlorite, vermiculite, kaolinite, amorphous and crystalline iron minerals) at the Koongarra ore deposit, Australia. The model considers the chlorite weathering process, its mechanism and rate, and assumes the presence of reversible and irreversible sorption sites in the secondary minerals. The calculated uranium concentrations at the two different sites in the minerals were compared with the results of sequential extraction experiments. Good agreement between the calculated and observed uranium concentrations was obtained only when an appropriate fraction of uranium is fixed to the irreversible sorption sites of the altered clay minerals. However, a conventional Kd model gave inconsistent uranium concentrations. The calculated results show that the crystalline iron minerals sorb uranium during all stages of weathering, and that the uranium fractionation among the minerals varies with time until the end of the weathering.

Characteristics of the migration of 85Sr and 137cs in a solution of pH 12 through coastal sandy soil have been investigated by both column and batch tests. Desorption behaviors of the 85Sr and 137Cs by the sandy soil in both column and batch tests were examined by sequential extraction techniques, in order to study difference in the adsorption behavior of the 85Sr and 137Cs under dynamic (column) and static (batch) conditions. The dominant components of the sandy soil to the adsorption of the 85Sr ancj 137Cs were tested in batch tests.

The adsorption of the 85Sr by the sandy soil was a function of pH, while that of the 137Cs was independent of pH of the solution. Most of the 85Sr was reversively adsorbed with the sandy soil under both static and dynamic conditions. Approximately 85 percent of the 137Cs was irreversibly sorbed by the sandy soil in the column test, which was greater than that in the batch test. The desorption behaviors of the 137Cs adsorbed by kaolinite and by sericite resembled that of the sandy soil. Most of the 85Sr was reversively adsorbed by kaolinite, chlorite, sericite, FeOOH, Ti02 and Mn02 which is similar to the desorption behavior of 85Sr by the sandy soil. The distribution coefficients of the 85Sr for kaolinite, FeOOH, Mn02 and Ti02 were larger by several times than those for the chlorite and the sericite.

Therefore, the dominant components of the sandy soil contributing to the adsorption of 137Cs would be sericite, and those of 85Sr would be kaolinite, FeOOH, Ti02 and Mn02.

The role of 234Th, a daughter nuclide of 238U having a half life of 24 days, in the migration of uranium series nuclides has been studied to understand the mechanism which gives a higher migration velocity of 238U than that of 234U. We assume that 234Th is adsorbed at two different sites; one, where 234Th is reversibly adsorbed, and the other, where 234Th is irreversibly fixed. Calculations have shown that the fixation of ^Th to a rock can cause the apparent migration velocity of 234U to be reduced compared to that of 238U and this agrees with observed field data. Changes in the fixation rate constants affect the relative mobility of 238U and 234U, and this can account for the different migration behavior at different depths in the Koongarra ore deposit.

The migration of an anionic species of 60Co through soil has been examined utilizing data on the migration of radionuclides leached from an aqueous waste disposal site. Correlation coefficients between concentrations of the anionic species of 60Co and those of the particulate, cationic and non-ionic species of 60Co reveal that the anionic species of 60Co was not interconverted from the other species during migration. The cross correlations of changes in the concentrations of the anionic species of 60Co with time between three different down gradient positions give a calculated retardation factor of the anionic species of 60Co of approximately 19, being 1200 times lower than the results of laboratory measurements. The average concentration distribution of the anionic species of 60Co suggests that the migration of the anionic species of 60Co consists of two migration fractions which were driven by different migration mechanisms.