• Nuclear Engineering and Technology
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• v.34 no.5
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• pp.517-531
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• 2002

The speciation and solubility of Am, Np, Pu and U have been analyzed by means of the geochemical code MUGREM, under the chemical conditions of domestic deep groundwater, in order to support the preliminary safety assessment for a Korean HLW disposal concept. Under the conditions of groundwaters studied, the stable solid phase is AmOHC $O_3$(s) or Am(OH)$_3$(s), soddyite((U $O_2$)$_2$ $SiO_2$.2$H_2O$) or N $a_2$ $U_2$ $O_{7}$ (c), Np(OH)$_4$(am), and Pu(OH)$_4$(am) for Am, U, Np, and Pu, respectively. The dominating aqueous species are as follows: the complexes of Am(III), Am(OH)$_2$$^{+}$ and Am(C $O_3$)$_2$$^{[-10]}$ , the complexes of U(VI), U $O_2$(OH)$_3$$^{[-10]}$ and U $O_2$(C $O_3$)$_3$$^{4-}$, the complexes of Np(IV), Np(OH)$_4$(aq) and Np(OH)$_3$C $O_3$, and the complexes of Pu(IV), Pu(OH)$_4$(aq) and Pu(OH)$_3$C $O_3$$^{[-10]}$ . The calculated solubilities exist between 1.9E-10 and 1.3E-9 mol/L for Am, between 5.6E-6 and 1.2E-4 mol/L for U, between 3.1E-9 and 1.3E-8 mol/L for Np, and between 6.6E-10 and 2.4E-10 mol/L for Pu, depending on groundwater conditions. The present solubilities of each actinide agree well with the results of other studies obtained under similar conditions.s.

• Journal of Soil and Groundwater Environment
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• v.22 no.5
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• pp.89-97
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• 2017

In this study, we evaluated effect of particle size on arsenic solid-state speciation and bioaccessibility in soils highly contaminated with arsenic from smelting and mining. Soils were partitioned into six particle size fractions ($2000-500{\mu}m$, $500-250{\mu}m$, $250-150{\mu}m$, $150-75{\mu}m$, $75-38{\mu}m$, <$38{\mu}m$), and arsenic solid-state speciation and bioaccessibility were characterized in each particle size fraction. Arsenic solid-state speciation was characterized via sequential extraction and XRD analysis, and arsenic bioaccessibility was evaluated by SBRC (Solubility Bioaccessibility Research Consortium) method. In smelter site soil, arsenic was mainly present as arsenic bound to amorphous iron oxides. Fine particle size fractions showed higher arsenic concentration, but lower arsenic bioaccessibility. On the other hand, arsenic in mine site soil showed highest concentration in largest particle size fraction ($2000-500{\mu}m$), while higher bioaccessibility was observed in smaller particle size fractions. Arsenic in mine site soil was mainly present as arsenolite ($As_2O_3$) phase, which seemed to affect the distribution of arsenic and arsenic bioaccessibility in different particle size fractions of the mine soil.

• Korean Journal of Soil Science and Fertilizer
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• v.41 no.1
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• pp.55-64
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• 2008

A detailed understanding and appreciation of the important mechanisms operating at the soil:root interface, commonly identified as the rhizosphere, is critical for evaluating the potential for particular plant species to be successfully used as part of a phytoremediation technique. For specific plants, mechanisms may exist to overcome the inherit limitation of the phytoremediation technique when poorly mobile soil metals are of interest. In the present study, the influence of root exudates on the rhizosphere chemistry of soil and consequential metal uptake were investigated following culture of vetiver grass (Vetiveria zizanioides), recognized as a promising plant for land stabilization, in three different long-term contaminated soils and one non-contaminated control soil. The soil solution pH increased (0.3-1.1 units) following vetiver grass culture and dissolved organic carbon (DOC) also significantly increased in all soils with the highest increase in PP02 (23 to $173mg\;L^{-1}$). Chemical changes are contributed to root exudation by vetiver grass when exposed to high concentration of heavy metals. Chemical changes, consequently, influenced metal (Cd, Cu, Pb, and Zn) solubility and speciation in the rhizosphere. The highest solubility was observed for soil Ko01 (eg. 2091 and $318{\mu}g\;L^{-1}$ for Cd and Pb, respectively). Initial heavy metal solubility in soils varied with soil and either increased or decreased following vetiver grass culture depending on the soil type. An increase in pH following plant culture generally resulted in a decrease in metal solubility, while elevated DOC due to root exudation resulted in an increase in metal solubility via the formation of metal-DOC complexes. Donnan speciation demonstrated a significant decrease in free Cd and Zn in the rhizosphere and the concentration of Cd, Pb, and Zn in vetiver grass shoot was highly correlated with soluble concentration rather than total soil metal concentration.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2017.10a
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• pp.137-138
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• 2017

The spectroscopic reference data for plutonium at different temperatures are necessary information for the chemical speciation and evaluation of thermodynamic data at elevated temperature. This work is the initial step to extend research activities for understanding the plutonium chemistry in aquatic solutions at high temperature. The hydrolysis of Pu(III) and the solubility of Pu(III) hydroxide at the elevated temperature will be discussed.

• Journal of the Speleological Society of Korea
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• no.92
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• pp.9-18
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• 2009

A number of closed metal mines act as point sources of contamination on nearby streams, soils and plants in our country. The contamination of twelve decomposed samples had earned from nine closed metal mines had been evaluated by TEA-3000. The contents of heavy metal with ion fraction exchange and carbonate fraction forms had been showed that the speciation of heavy metals represented with easy solubility, mobility and bioavailable of plants, and in case of sulfide compounds and organic residuals forms are related with the speciation of metals which may be stable forms because of strong bindable capacity. Also heavy metals elements in mosts of mines got with relative stable within crystal lattice, but results of trace element analyser showed that, in the most of tailings from mine areas, large portions of concentration of heavy metals were explained as stable from, sulfides/ organics and residual. In tailing from Imchun mines, the concentrations extracted by water were relatively high as compared with other mine areas whose total concentrations were very high because of large quantities of exchangeable ions and carbonates and low soil pH. Danger Index (D.I.) suggested in this study was based on the cumulative concentrations of step 1 and 2 from the result of trace element analyser. When the soil pH was considered, this index became better indicator to determine the priority for the remediation of mine area.

• Membrane and Water Treatment
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• v.1 no.4
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• pp.231-251
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• 2010

The sulfatation of chitosan, by reaction with chlorosulfonic acid under controlled conditions, allowed increasing the pH range of chitosan solubility. The biopolymer was characterized using FTIR and $^{13}C$-NMR spectroscopy, elemental analysis and titration analysis and it was tested for mercury recovery by polymer enhanced ultrafiltration (PEUF). In slightly alkaline conditions (i.e., pH 8) mercury recovery was possible and at saturation of the polymer the molar ratio $-NH_2$/Hg(II) tended to 2.6. Polymer recycling was possible changing the pH to 2 and the polymer was reused for 3 cycles maintaining high metal recovery. The presence of chloride ions influences metal speciation and affinity for the polymer and "playing" with metal speciation allowed using the PEUF process for mercury separation from cadmium; at pH 11 the formation of hydroxo-complexes of Hg(II) limits it retention. Cake formation reveals the predominant controlling step for permeation flux.

• 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.

• Nuclear Engineering and Technology
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• v.41 no.6
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• pp.867-874
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• 2009

Solubility of a radionuclide is important for defining the release source term of a radioactive waste in the safety and performance assessments of a radioactive waste repository. When the pH and redox potential of the KURT groundwater were changed by an electrical method, the concentrations of uranium and thorium released from $UO_2$(cr) and $ThO_2$(cr) at alkali pH(8.1 ${\sim}$ 11.4) and reducing potential (Eh < -0.2 V) conditions were less than $10^{-7}mole/L$. Unexpectedly, the concentration of tetravalent thorium is slightly higher than that of uranium at pH = 8.1 and Eh= -0.2 V conditions, and this difference may be due to the formation of hydroxide-carbonate complex ions. When $UO_2$(s) and $UO_2$(am, hyd.), and $ThO_2$(s) and $Th(OH)_4(am)$ were assumed as solubility limiting solid phases, the concentrations of uranium and thorium in the KURT groundwater calculated by the PHREEQC code were comparable to the experimental results. The dominating aqueous species of uranium and thorium were presumed as $UO_2(CO_3)_3^{4-}$ and $Th(OH)_3CO_3^-$ at pH = 8.1 ${\sim}$ 9.8, and $UO_2(OH)_3^-$ and $Th(OH)_4(aq)$ at pH = 11.4.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.3
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• pp.189-197
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• 2007

The solubility of U(VI) hydrolysis products was determined by using a laser-induced breakdown detection (LIBD) technique. The experiments were carried out at uranium concentrations in range from $2{\times}10^{-4}\;M\;to\;4{\times}10^{-6}\;M$, pH values between 3.8 and 7.0, the constant ionic strength of 0.1 M $NaClO_4$ and the temperature of $25.0{\pm}0.1^{\circ}C$. The solubility product of U(VI) hydrolysis products was calculated from LIBD results by using the hydrolysis constants selected in NEA-TDB. The solubility product extrapolated to zero ionic strength, ${\log}K^{\circ}_{sp}=-22.85{\pm}0.23$ was calculated by using a specific ion interaction theory (SIT). The spectral features of ionic species in uranium solutions were investigated by using a conventional UV-visible absorption spectrophotometer and a fluorophotometer, respectively, $(UO_2)_2(OH)_2^{2+}\;and\;(UO_2)_3(OH)_5^+$ were dominant species at uranium concentration of $2{\times}10^{-4}\;M$.

• Nuclear Engineering and Technology
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• v.38 no.6
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• pp.459-482
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• 2006

A geochemical approach to the long-term safety of waste disposal is discussed in connection with the significance of actinides, which shall deliver the major radioactivity inventory subsequent to the relatively short-term decay of fission products. Every power reactor generates transuranic (TRU) elements: plutonium and minor actinides (Np, Am, Cm), which consist chiefly of long-lived nuclides emitting alpha radiation. The amount of TRU actinides generated in a fuel life period is found to be relatively small (about 1 wt% or less in spent fuel) but their radioactivity persists many hundred thousands years. Geological confinement of waste containing TRU actinides demands, as a result, fundamental knowledge on the geochemical behavior of actinides in the repository environment for a long period of time. Appraisal of the scientific progress in this subject area is the main objective of the present paper. Following the introductory discussion on natural radioactivities, the nuclear fuel cycle is briefly brought up with reference to actinide generation and waste disposal. As the long-term disposal safety concerns inevitably with actinides, the significance of the aquatic actinide chemistry is summarized in two parts: the fundamental properties relevant to their aquatic behavior and the geochemical reactions in nanoscopic scale. The constrained space of writing allows discussion on some examples only, for which topics of the primary concern are selected, e.g. apparent solubility and colloid generation, colloid-facilitated migration, notable speciation of such processes, etc. Discussion is summed up to end with how to make a geochemical approach available for the long-term disposal safety of nuclear waste or for the performance assessment (PA) as known generally.