• Nuclear Engineering and Technology
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• v.54 no.5
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• pp.1616-1622
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• 2022

Selenium has been identified as an element of interest for the safety assessment of a deep geological repository (DGR) for used nuclear fuel. In Canada, groundwaters at DGR depths in sedimentary rocks have been observed to have a high ionic strength. This paper examines the sorption behavior of Se(-II) onto illite, MX-80 bentonite, Queenston shale, and argillaceous limestone in Na-Ca-Cl solutions of varying ionic strength (0.1-6 mol/kgw (m)) and across a pH range of 4-9. Little ionic strength dependence for Se(-II) sorption onto all solids was observed except that sorption at high ionic strength (6 m) was generally slightly lower than sorption at low ionic strength (0.1 m). Illite and MX-80 exhibited the expected results for anion sorption, while shale and limestone exhibited more constant sorption across the pH range tested. A non-electrostatic surface complexation model successfully predicted sorption of Se(-II) onto illite and MX-80 using the formation of an inner-sphere surface complex and an outer-sphere surface complex. Optimized values for the formation reactions of these surface species were proposed.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.21 no.4
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• pp.427-438
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• 2023

Thermodynamic sorption modeling can enhance confidence in assessing and demonstrating the radionuclide sorption phenomena onto various mineral adsorbents. In this work, Ca-montmorillonite was successfully purified from Bentonil-WRK bentonite by performing the sequential physical and chemical treatments, and its geochemical properties were characterized using X-ray diffraction, Brunauer-Emmett-Teller analysis, cesium-saturation method, and controlled continuous acid-base titration. Further, batch experiments were conducted to evaluate the adsorption properties of Cs(I) and Sr(II) onto the homoionic Ca-montmorillonite under ambient conditions, and the diffuse double layer model-based inverse analysis of sorption data was performed to establish the relevant surface reaction models and obtain corresponding thermodynamic constants. Two types of surface reactions were identified as responsible for the sorption of Cs(I) and Sr(II) onto Ca-montmorillonite: cation exchange at interlayer site and complexation with edge silanol functionality. The thermodynamic sorption modeling provides acceptable representations of the experimental data, and the species distributions calculated using the resulting reaction constants accounts for the predominance of cation exchange mechanism of Cs(I) and Sr(II) under the ambient aqueous conditions. The surface complexation of cationic fission products with silanol group slightly facilitates their sorption at pH > 8.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.20 no.1
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• pp.1-12
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• 2022

Bentonite is the most probable candidate to be used as a buffer in a deep geological repository with high swelling properties, hydraulic conductivity, thermal conductivity, and radionuclide sorption ability. Among them, the radionuclide sorption ability prevents or delays the transport of radionuclides into the nearby environment when an accident occurs and the radionuclide leaks from the canister, so it needs to be strengthened in terms of long-term disposal safety. Here, we proposed a surface modification method in which some inorganic additives were added to form NaP zeolite on the surface of the bentonite yielded at Yeonil, South Korea. We confirmed that the NaP zeolite was well-formed on the bentonite surface, which also increased the sorption efficiency of Cs and Sr from groundwater conditions. Both NaP and NaX zeolite can be produced and we have demonstrated that the generation mechanism of NaX and NaP is due to the number of homogeneous/heterogeneous nucleation sites and the number of nutrients supplied from an aluminosilicate gel during the surface modification process. This study showed the potential of surface modification on bentonite to enhance the safety of deep geological radioactive waste repository by improving the radionuclide sorption ability of bentonite.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.1
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• pp.1-7
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• 2021

The pH dependence of sorption distribution coefficient (Kd) of Np(IV) on MX-80 in Ca-Na-Cl type solution with the ionic strength of 0.3 M, which was similar to one of the reference groundwaters in crystalline rock, was experimentally investigated under the reducing conditions. The overall trend of Kd on MX-80 was independent of pH at 5 ≤ pH ≤ 10 but increased as pH increased at pH ≤ 5. The 2-site protolysis non-electrostatic surface complexation and cation exchange model was applied to the experimentally measured pH dependence of Kd and the optimized surface complexation constants of Np(IV) sorption on MX-80 were estimated. The values of surface complexation constants in this work agreed relatively well with those in the Na-Ca-Cl solution previously evaluated, suggesting that compared to Na+, the competition of Ca2+ with Np(IV) for surface complexation on MX-80 was not much strong in Ca-Na-Cl solution. The sorption model well predicted the pH dependence of Kd values but slightly overestimated the sorption at the low pH region.

• Journal of the Korean earth science society
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• v.43 no.4
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• pp.532-538
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• 2022

Under anoxic conditions, this study investigated removal of dissolved As(III) by Si and Al oxides including natural sand, chemically washed sand (silica), alumina, and activated alumina. Despite the similar surface area, natural sand showed greater extents of As(III) sorption than chemically washed sand. This was likely due to the high reactivity of Fe(oxyhydr)oxide impurities on the surface of natural sand. For both sands, As(III) sorption was the greatest at pH 7.1, in agreement with the weakly dissociating tendency of arsenous acid. Also, the least sorption was observed at pH 9.6. At basic pH, elevated silicate, which originated from the dissolution of silica in sands, would compete with As(III) for sorption. Due to the highest surface area, activated alumina was found to quantitatively immobilize the initially added As(III) (6.0×10^-7-2.0×10^-5 M). Alumina showed As(III) sorption compared to or greater than chemically washed sand, although the former had less than 6% of the surface of area the latter. The greater reactivity of alumina than chemically washed sand can be explained by using the shared charge of oxygen.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.09a
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• pp.132-135
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• 2003

Solution chemistry, sorbate chemistry, and sorbent chemistry were widely investigated to find important factors that affect PAH sorption on mineral surfaces and to elucidate its microscopic mechanism. The solution chemistry, pH and ionic strength caused measurable change of HOC sorption reaction to minerals. The detectable change of Ka occurred at a pH region crossing the PZC (Point of Zero Charge) of each mineral. The PAH hydrophobicity, one of sorbate chemistry, was observed to have a strong correlation with PAM sorption to mineral. Mineral surface area was not found to be a predominant factor controlling PAH sorption. The mineral type might be more likely to play a crucial role in controlling the PAH sorption behavior. The CEC (Cation Exchange Capacity) of mineral, representing surface charge density, has meaningful correlation with regression slope of sorption coefficients (log $K_{d}$) versus aqueous activity coefficients (log Υ$_{w}$).).).

• Carbon letters
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• v.9 no.4
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• pp.275-282
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• 2008

Chemically activated carbons were prepared from maize cobs, using phosphoric acid of variable concentration. The textural parameters of the activated carbons were determined from the nitrogen adsorption isotherms measured at 77 K. The chemistry of the carbon surface was determined by measuring the surface pH, the pHPZC and the concentration of the carbon - oxygen groups of the acid type on the carbon surface. Kinetics of Cr(VI) sorption/reduction was investigated at 303 K. Two processes were investigated in terms of kinetics and equilibrium namely; Cr(VI) removal and chromium sorption were studied at various initial pH (1-7). Removal of Cr(VI) shows a maximum at pH 2.5. At pH<2.5, sorption decreases because of the proton competition with evolved Cr(III) for ion exchange sites. The decrease of sorption at pH>2.5 is due to proton insufficiency and to the decrease of the extent of Cr(VI) reduction. The chemistry of the surface of activated carbon is an important factor in determining its adsorption capacity from aqueous solutions particularly when the sorption process involves ion exchange.

• Proceedings of the Korean Nuclear Society Conference
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• 1998.05b
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• pp.453-457
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• 1998

The sorption of UO$_2$$^{2+}$showed ionic strength independece for goethite and dependence for kaolinite. In the presence of carbonate, the sorption decreased in the weakly alkaline pH range becase of the formation of aqueous U(VI)-carbonate complexes. The sorption of UO$_2$$^{2+}$onto goethite and kaolinite under various experimental conditions was successfully interpreted using a surface complexation modeling, named triple layer model (TLM). The best fit to the experimental data was obtained by the FITEQL program, and then evaluated with available spectroscopic data. The results showed the versatility of surface complexation modeling over empirical one to predict UO$_2$$^{2+}$ sorption behavior.avior.

• Nuclear Engineering and Technology
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• v.53 no.3
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• pp.894-900
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• 2021

This paper examines sorption of Pd(II) onto illite, MX-80 bentonite, and Queenston shale in Na-Ca-Cl solutions of varying ionic strength (IS) from 0.01 to 6.0 mol/L (M) and pH_c ranging from 3 to 9 under atmospheric conditions. A 2-site protolysis non-electrostatic surface complexation and cation exchange model was applied to the Pd sorption onto illite and MX-80 using PHREEQC, and the model results were compared to the experimental ones obtained in this work. Surface complexation and cation exchange constants were estimated for both illite and MX-80 through the optimization process to bring the predicted distribution coefficients from the model into alignment with the experimentally derived values. These optimized surface complexation constants were compared to existing linear free energy relationships (LFER).

• Proceedings of the Korean Environmental Sciences Society Conference
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• 1998.10a
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• pp.2-4
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• 1998

Proliferation of Nocardia amarae cells in activated sludge has often been associated with the generation of nuisance foams. Despite intense research activities in recent years to examine the causes and control of Nocardia foaming in activated sludge, the foaming continued to persist throughout the activated sludge treatment plants in United States. In addition to causing various operational problems to treatment processes, the presence of Nocardia may have secondary effects on the fate of heavy metals that are not well known. For example, for treatment plants facing more stringent metal removal requirements, potential metal removal by Nocardia cells in foaming activated sludge would be a welcome secondary effect. In contrast, with new viosolid disposal regulations in place (Code o( Federal Regulation No. 503), higher concentration of metals in biosolids from foaming activated sludge could create management problems. The goal of this research was to investigate the metal sorption property of Nocardia amarae cells grown in batch reactors and in chemostat reactors. Specific surface area and metal sorption characteristics of N. amarae cells harvested at various growth stages were compared. Three metals examined in this study were copper, cadmium and nickel. Nocardia amarae strain (SRWTP isolate) used in this study was obtained from the University of California at Berkeley. The pure culture was grown in 4L batch reactor containing mineral salt medium with sodium acetate as the sole carbon source. In order to quantify the sorption of heavy metal ions to N amarae cell surfaces, cells from the batch reactor were harvested, washed, and suspended in 30mL centrifuge tubes. Metal sorption studies were conducted at pH 7.0 and ionlc strength of 10-2M. The sorption Isotherm showed that the cells harvested from the stationary and endogenous growth phase exhibited significantly higher metal sorption capacity than the cells from the exponential phase. The sequence of preferential uptake of metals by N. amarae cells was Cu>Cd>Ni. The specific surFace area of Nocardia cells was determined by a dye adsorption method. N.amarae cells growing at ewponential phase had significantly less specific surface area than that of stationary phase, indicating that the lower metal sorption capacity of Nocardia cells growing at exponential phase may be due to the lower specific surface area. The growth conditions of Nocardia cells in continuous culture affect their cell surface properties, thereby governing the adsorption capacity of heavy metal. The comparison of dye sorption isotherms for Nocardia cells growing at various growth rates revealed that the cell surface area increased with increasing sludge age, indicating that the cell surface area is highly dependent on the steady-state growth rate. The highest specific surface area of 199m21g was obtained from N.amarae cell harvested at 0.33 day-1 of growth rate. This result suggests that growth condition not only alters the structure of Nocardia cell wall but also affects the surface area, thus yielding more binding sites of metal removal. After reaching the steady-state condition at dilution rate, metal adsorption isotherms were used to determine the equilibrium distributions of metals between aqueous and Nocardia cell surfaces. The metal sorption capacity of Nocardia biomass harvested from 0.33 day-1 of growth rate was significantly higher than that of cells harvested from 0.5- and 1-day-1 operation, indicatng that N.amarae cells with a lower growth rate have higher sorpion capacity. This result was in close agreement with the trend observed from the batch study. To evaluate the effect of Nocardia cells on the metal binding capacity of activated sludge, specific surface area and metal sorption capacity of the mixture of Nocardia pure cultures and activated sludge biomass were determined by a series of batch experiments. The higher levels of Nocardia cells in the Nocardia-activated sludge samples resulted in the higher specific surface area, explaining the higher metal sorption sites by the mixed luquor samples containing greater amounts on Nocardia cells. The effect of Nocardia cells on the metal sorption capacity of activated sludge was evaluated by spiking an activated sludge sample with various amounts of pre culture Nocardia cells. The results of the Langmuir isotherm model fitted to the metal sorption by various mixtures of Nocardia and activated sludge indicated that the mixture containing higher Nocardia levels had higher metal adsorption capacity than the mixture containing lower Nocardia levels. At Nocardia levels above 100mg/g VSS, the metal sorption capacity of activate sludge increased proportionally with the amount of Noeardia cells present in the mixed liquor, indicating that the presence of Nocardia may increase the viosorption capacity of activated sludge.