Multiple sorptive sites on natural illitic clays (e.g., frayed edge [FES], type II [TS], and planar sites [PS]) play an important role to diverse 137Cs immobilization in soil and aquifer environments. This study investigated the Cs sorption capabilities of 10 natural illitic clays at ranged Cs concentrations (1 ×10−7 to 1×10−3 mol·L−1) under various competing potassium concentration (distilled water to 1×10−1 mol·L−1). Additionally, multisite cation exchange model was performed to evaluate the best-fit sorption model and optimize the sorption capacities and affinities of multiple sorptive sites for Cs. Here, the experimental Cs sorption isotherms varied among 10 illtic clays, indicating different sorption capacities of Cs on illitic clays. The best-fit sorption model exhibited that variable Cs sorption of 10 illitic clays was significantly related to the sorption capacities at the FES (1.76 × 10−5 to 1.12×10−4 eq·kg−1), TS (1.59×10−3 to 9.76×10−3 eq·kg−1), and PS (2.14×10−2 to 1.51×10−1 eq·kg−1), respectively. The FES predominantly contributed to Cs sorption at low aqueous concentrations, whereas the TS and PS sorbed Cs at high concentrations. These sorption capabilities of multiple sorptive sites were correlated to illite contents and crystallinity of illitic clays, implicating that such parameters could be key factors to predict the Cs sorption for natural illitic clays in soil and aquifer environments. Finally, 1-D transport simulations represented that the severe Cs retardation occurred at low Cs concentration, implying that the FES predominantly affected to Cs transport in actual radioactive contamination sites (i.e., where low Cs concentration prevails), compared to the TS and/or PS.

A deep geological disposal system, which consists of the engineered and natural barrier components, is the most proven and widely adopted concept for a permanent disposal of the high level radioactive waste (HLW) thus far. The clay-based engineered barrier is designed to not only absorb mechanical stress caused by the geological activities, but also prevent inflow of groundwater to canister and outflow of radionuclides by providing abundant sorption sites. The principal mineralogical constituent of the clay material is montmorillonite, which is a 2:1 phyllosilicate having two tetrahedral sheets of SiO2 sandwiching an octahedral sheet of Al2O3. The stacking of SiO2 and Al2O3 sheets form the layered structures, and ion-exchange and water uptake reactions occur in the interlayer space. In order to reliably assess the radionuclide retention capacity of engineered barrier under wide geochemical conditions relevant to the geological disposal environments, sorption mechanisms between montmorillonite and radionuclides should be explicitly investigated in advance. Thus far, sorption behavior of mineral adsorbents with radionuclides has been quantified by the sorption-desorption distribution coefficient (Kd), which is simply defined as the ratio of radionuclide concentration in the solid phase to that in the equilibrium solution; the Kd value is conditional, and there have been scientific efforts to develop geochemically robust bases for parameterizing the sorption phenomena more reliably. In this framework, application of thermodynamic sorption model (TSM), which is theoretically based on the concept of widely accepted equilibrium models for aquatic chemistry, offers the potential to improve confidence in demonstration of radionuclide sorption reactions on the mineral adsorbents. Specifically, it is generally regarded in the TSM that coordination of radionuclides on montmorillonite takes place at the surficial aluminol and silanol groups while their ion-exchange reactions occur in the interlayer space also. The effects of electrical charge on the surface reactions are additionally corrected in accordance with the numerous theories of electrochemical interface. The present work provides an overview of the current status of application of TSM for quantifying sorption behaviors of radionuclides on montmorillonite and experimental results for physical separation and characterization of Ca-montmorillonite from the newly adopted reference bentonite (Bentonil- WRK) by means of XRD, BET, FTIR, CEC measurement, and acid-base titration. The determined mineralogical and chemical properties of the montmorillonite obtained will be used as input parameters for further sorption studies of radionuclides with the Bentonil-WRK montmorillonite.

Heavy metal pollution has a harmful impact on human health and is regarded as a vital problem. Preparation of a novel, low cost bio-sorbent for heavy metal sorption is the main target of this research. Non-living Chlorella Vulgaris Alga/Date pit activated carbon composite (1:1), (CV/AC), is a novel bio-sorbent prepared by the wet-chemical method for sorption of Pb (II) and Sr (II) from aqueous media. The optimum pH for sorption reaction is 5 and the equilibrium time is achieved within 1 h. The sorption efficiencies are 90.5% for Pb(II) and 95.7% for Sr(II) with initial concentration Co 10 mg L– 1 at 298 K. The monolayer sorption capacities of CV/AC composite at 298 K and pH = 5 were 6.34 ± 0.059, 5.97 ± 0.22 mg g– 1. The saturation capacities were 98.5 and 125 mg g– 1 for Pb (II) and Sr (II), respectively after 10 days. The sorption process is a spontaneous and endothermic reaction. It follows a pseudo-2nd-order mechanism. The results are suggestive of the need to adopt CV/AC composite as a potential bio-sorbent of Pb (II) and Sr (II) for waste water treatment.

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.

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.

스트론튬(90Sr)과 니켈(59Ni)은 처분안전성평가에서 중요하게 다루는 핵종들이다. 지하에서 방사성핵종의 이동을 저지하기 위한 다양한 시도가 이루어지고 있는데, 처분시스템에서 용기와 부식반응으로 생기는 광물들 중에 핵종들과 반응성이 뛰어난 광물들이 존재하는 것이 알려졌다. 이들 중에서 철-황화합광물인 맥키나와이트(FeS)를 선정하여 스트론튬, 니켈과 수착 실험을 하였다. 심부지하에서 환원 알카리 환경을 고려하여, pH 8 ~ 12까지 조건에서 pH에 따른 수착영향을 살펴보았다. 실험결과, 스트론튬은 낮은 알카리영역에서 수착능이 저조하였지만, 니켈은 전 실험영역에서 높은 수착능을 보였다. 또, 두 핵종 모두 알카리 조건에서 pH가 증가할수록 수착량(Kd)이 증가하였는데, 이는 pH가 증가하면서 풍부해진 OH‐이온이 광 물표면에 수소나 양이온과 결합해 탈착하면서 광물표면에 전기음성도가 증가해 양이온인 스트론튬과 니켈을 전기적 인력으로 끌어당기기 때문으로 여겨진다.