• Economic and Environmental Geology
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• v.41 no.6
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• pp.719-729
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• 2008

In this study, the speciation, adsorption, and transport of uranium in groundwater environments were simulated using geochemical models. The retarded transport of uranium by adsortption was effectively simulated using 3-D groundwater flow and reactive transport models. The results showed that most uranium was adsorbed(up to 99.5%) in a neutral pH(5.5$pCO_2(10^{-3.6}atm)$ condition. Under the higher $pCO_2(10^{-2.5}atm)$ condition, however, the pH range where most uranium was absorbed was narrow from 6 to 7. Under very low $pCO_2(10^{-4.5}atm)$ condition, uranium was mostly absorbed in the relatively wide pH range between 5.5 and 8.5. In the model including anion complexes, the uranium adsorption decreased by fluoride complex below the pH of 6. The results of this study showed that uranium transport is strongly affected by hydrochemical conditions such as pH, $pCO_2$, and the kinds and concentrations of anions($Cl^-$, ${SO_4}^{2-}$, $F^-$). Therefore, geochemical models should be used as an important tool to predict the environmental impacts of uranium and other hazardous compounds in many site investigations.

• Economic and Environmental Geology
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• v.42 no.5
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• pp.471-477
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• 2009

An experimental removal of dissolved uranium (U) exsiting as uranyl ion (${UO_2}^{2+}$) was carried out using Shewanella p., iron-reducing bacterium. By the microbial reductive reaction, initial U concentration ($50{\mu}M$) was constantly decreased, and most U were removed from solution after 2 weeks. Major mechanism that U was removed from the solution was adsorption, precipitation and mineralization on the microbe surface. Under the transmission electron microscopy, the U adsorbed on the microbe was observed as being crystallized and eventually enlarged to several ${\mu}m$ sizes of minerals by combining with individual microbes and organic exudates. It seems that such U growth and mineralization on the microbial surface could affect the U behavior in a radioactive waste disposal site. Thus, the biogechemical reaction of metal-reducing bacteria observed in this experiment could give an affirmative measure that the microbial activity may retard U movement in subsurface environment.

• Economic and Environmental Geology
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• v.43 no.3
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• pp.223-233
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• 2010

The effects of extracellular polymeric substances (EPS) of Pseudomonas aeruginosa on adsorption and redox state alteration of dissolved As, Cr and U were investigated through batch experiments. Surfaces of bacterial cells were either vigorously washed or unwashed. Solutions of As(V), Cr(VI) and U(VI) were inoculated with the bacterial cells under no nutrient condition, and total aqueous concentrations and redox state alteration were monitored over time. No As adsorption occurred onto bacteria or EPS; however, unwashed bacteria reduced about 60% As(V) to As(III). Unwashed bacteria also led to removal of 45% total dissolved Cr and reduction of 64% Cr(VI). About 80% U(VI) was removed from solution with unwashed bacteria as well. Such electrochemical reduction of the elements was likely due to reducing capacity of EPS itself or detoxifying reduction of the bacteria which kept their viability under protection of EPS. The results indicated that bacterial biofilm may significantly control the redox state and subsequent mobility of As, Cr and U in natural geologic settings.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.4 no.3
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• pp.235-243
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• 2006

In this study, an experimental study on the sorption properties of uranium(VI) onto a bentonite colloid generated from Gyeongju bentonite which is a potential buffer material in a high-level radioactive waste repository was performed as a function of the pH and the ionic strength. The bentonite colloid prepared by separating a colloidal fraction was mainly composed of montmorillonite. The concentration and the size fraction of the prepared bentonite colloid measured using a gravitational filtration method was about 5100 ppm and 200-450 nm in diameter, respectively. The amount of uranium removed by the sorption reaction bottle walls, by precipitation, and by ultrafiltration was analyzed by carrying out some blank tests. The removed amount of uranium was found not to be significant except the case of ultrafiltration at 0.001 M $NaClO_4$. The ultrafiltration was significant in the lower ionic strength of 0.001 M $NaClO_4$ due to the cationic sorption onto the ultrafilter by a surface charge reversion. The distribution coefficient $K_d$ (or pseudo-colloid formation constant) of uranium(VI) for the bentonite colloid was about $10^4{\sim}10^7mL/g$ depending upon pH and ionic strength of $NaClO_4$ and the $K_d$ was highest in the neutral pH around 6.5. It is noted that the sorption of uranium(VI) onto the bentonite colloid is closely related with aqueous species of uranium depending upon geochemical parameters such as pH, ionic strength, and carbonate concentration. As a consequence, the bentonite colloids generated from a bentonite buffer can mobilize the uranium(VI) as a colloidal form through geological media due to their high sorption capacity.

• Analytical Science and Technology
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• v.23 no.6
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• pp.566-571
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• 2010

This paper describes the sorption behaviors of aqueous uranium ions on the K-birnessite. K-birnessite was synthesized by adding a concentrated HCl to an aqueous solution of $KMnO_4$. Physicochemical characteristics of the K-birnessite, such as structure, specific surface area and surface charge, were investigated. K-birnessite is a layered material and the $K^+$ ions exist in the interlayer of layered K-birnessite. BET specific surface area of the K-birnessite was 38.30 m2/g. The surface charge of K-birnessite was $-1.65\;C/m^2$ at pH 5.00 and ionic strength of 0.010 M $NaClO_4$, at which the sorption experiments of uranium ions were carried out. Uranium ions were incorporated into the interlayer of the K-birnessite by cation-exchange reaction with $K^+$ ions, and the distribution coefficient is quite similar to those of common ion-exchange materials. The results might be applicable in the retardation of migration of radioactive materials from the underground disposal site of high-level radioactive waste.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.847-870
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• 2023

The safe disposal of high-level radioactive waste requires accurate predictions of the long-term geochemical behavior of radionuclides. To achieve this, the present study was conducted to model geochemical behaviors of uranium (U), plutonium (Pu), and palladium (Pd) under different hydrogeochemical conditions that represent deep groundwater in Korea. Geochemical modeling was performed for five types of South Korean deep groundwater environment: high-TDS saline groundwater (G1), low-pH CO₂-rich groundwater (G2), high-pH alkaline groundwater (G3), sulfate-rich groundwater (G4), and dilute (fresh) groundwater (G5). Under the pH and Eh (redox potential) ranges of 3 to 12 and ±0.2 V, respectively, the solubility and speciation of U, Pu, and Pd in deep groundwater were predicted. The result reveals that U(IV) exhibits high solubility within the neutral to alkaline pH range, even in reducing environment with Eh down to -0.2 V. Such high solubility of U is primarily attributed to the formation of Ca-U-CO₃ complexes, which is important in both G2 located along fault zones and G3 occurring in granitic bedrocks. On the other hand, the solubility of Pu is found to be highly dependent on pH, with the lowest solubility in neutral to alkaline conditions. The predominant species are Pu(IV) and Pu(III) and their removal is predicted to occur by sorption. Considering the migration by colloids, however, the role of colloid formation and migration are expected to promote the Pu mobility, especially in deep groundwater of G3 and G5 which have low ionic strengths. Palladium (Pd) exhibits the low solubility due to the precipitation as sulfides in reducing conditions. In oxidizing condition, anionic complexes such as Pd(OH)₃^-, PdCl₃(OH)₂^-, PdCl₄^2-, and Pd(CO₃)₂^2- would be removed by sorption onto metal (hydro)oxides. This study will improve the understanding of the fate and transport of radionuclides in deep groundwater conditions of South Korea and therefore contributes to develop strategies for safe high-level radioactive waste disposal.

• Economic and Environmental Geology
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• v.12 no.1
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• pp.41-49
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• 1979

A literature review is made on the physical and chemical characteristics of clay minerals in acidic solutions from the mineralogical and hydrometallurgical viewpoints. Some of the important characteristics of clays are their ability to cation exchange, swelling, and incongruent dissolution in acidic solutions. Various clay minerals can take up metallic ions from solution via cation exchange mechanism. Generally, cation exchange capacity increases in the following order : kaolinite, halloysite, illite, vermiculite, and montmorillonite. In acidic solutions, the cation uptake such as copper by clay minerals is strongly inhibited by hydrogen and aluminum ions and thus is not economically significant factor for recovery of metals such as uranium and copper. In acidic solutions, the cation uptake is substial. Swelling is minimal at lower pH, possibly due to lattice collapse. Swelling may be controllable with montmorillonite type clays by exchanging interlayer sodium with lithium and/or hydroxylated aluminum species. The effect of add on clay minerals are : 1. Division of aggregates into smaller plates with increase in surface area and porosity. 2. Clay-acid reactions occur in the following order: (i) $H^+$ replacement of interlayer cations, (ii) removal of octahedral cations, such as Al, Fe, and Mg, and (iii) removal of tetrahedral Al ions. Acid attack initiates, around the edges of the clay particles and continued inward, leaving hydrated silica gel residue around the edges. 3. Reaction rates of (ii) and (iii) are pseudo-1st order and proportional to acid concentration. Rate doubles for every temperature increment of $10^{\circ}C$. Implications in in-situ leaching of copper or uranium with acid are : 1. Over the life span of the operation for a year or more, clays attacked by acid will leave silica gel. If such gel covers the surface of valuable mineral surfaces being leached, recovery could be substantially delayed. 2. For a copper deposit containing 0.5% each of clay minerals and recoverable copper, the added cost due to clay-acid reaction is about 1.5c/lb of copper (or 0.93 lbs of $H_2SO_4/1b$ of copper). This acid consumption by clay may be a factor for economic evaluation of in-situ leaching of an oxide copper deposit.