The permanent disposal of discharged spent nuclear fuel (SNF) and contaminated radioactive waste generated from the subsequent chemical treatments of SNF has become a serious pending issue in many countries that operate the nuclear power plants. Among the diverse engineering solutions proposed for the disposal of high-level radioactive waste (HLW), deep geological disposal (DGD) has been considered as the most proven and safe option to prevent any significant release of radionuclides into the biosphere and to predictably ensure the long-term performance of disposal system. The DGD system consists of multiple structural components; the bentonite clay-based buffer and tunnel backfills are designed to perform the primary hydrogeochemical functions of 1) inhibiting the ingress of groundwater and reactive substances that could compromise the integrity of canister and 2) retarding the migration of released radionuclides into biosphere by providing the sufficient chemisorption sites. Montmorillonite, which is a 2:1 phyllosilicate mineral belonging to smectite group, constitutes the majority of bentonite, and it mainly predominate the swelling and chemisorption capacities of the clay material. Thus, it is essentially required to thoroughly understand the chemical interactions of major radionuclides and other important substances with montmorillonite in advance to accurately evaluate the long-term retention performance of engineered barriers and to reduce the uncertainties in the safety assessment of a deep geological repository (DGR) ultimately. Thus far, sorption of dissolved species onto mineral adsorbents has been generally described and quantified using the simple sorption-desorption distribution coefficient (Kd) concept; since any specific reaction mechanisms are not considered and reflected in the Kd concept, an empirical Kd value is intrinsically dependent on the aqueous conditions under which it was measured. In this framework, substantial scientific efforts have been made to develop a robust basis for geochemically parametrizing the sorption phenomena more reliably, and the application of thermodynamic sorption modeling (TSM), which is based on the chemical principle of mass action laws, has been studied with the aim of improving overall confidence in the description of radionuclide migration under a wide range of aquatic conditions. The disposal performance demonstration R&D division of KAERI introduced a new reference Ca-bentonite clay called Bentonil-WRK (Clariant Korea) for HLW disposal research in 2021 as the domestic Ca-bentonite sources have being depleted. We successfully separated and purified Ca-montmorillonite from the Bentonil-WRK clay, and its geochemical characteristics were meticulously studied by means of XRD, BET, CEC, FT-IR analyses and controlled acid-base titration. In this work, chemical sorption behaviors of aqueous iodide and benzoate, which are a major fission product in HLW and a model ligand of complex natural organic matters present in the deep geological environment, onto the purified Camontmorillonite were assessed under ambient conditions of S/L = 5 g/L, I = 0.01 M CaCl2, pH = 4- 9, pCO2 = 10-3.4 atm, and T = 25°C. Further, their unique adsorption envelopes and corresponding thermodynamic reaction constants refined from the diffuse double layer model (DDLM)-based inverse modeling of experimental sorption data were discussed.

Bentonite is a potential buffer material of multi-barrier systems in high-level radioactive wastes repository. Montmorillonite, the main constituent of the bentonite, is 2:1 type aluminosilicate clay mineral with high swelling capacity and low permeability. Montmorillonite alteration under alkaline and saline conditions may affect the physico-chemical properties of the bentonite buffer. In this study, montmorillonite alteration by interaction with synthetic alkaline and saline solution and its retention capacity for cesium and iodide were investigated. The experiments were performed in three different batches (Milli-Q water, alkaline water, and saline water) doped with cesium and iodide for 7 days. Alteration characteristics and nuclide retention capacity of original- and reacted bentonite was analyzed by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), Nuclear Magnetic Resonance (NMR) and Cation Exchange Capacity (CEC) analysis. From the results, cesium retention occurred differently depending on the presence of competing ions such as K, Na, and Mg ions in synthetic solutions, while iodide was negligibly removed by bentonite. Montmorillonite alteration mainly occurred as cation exchange and zeolite minerals such as merlinoite and mordenite were new-formed during alkaline alteration of the montmorillonite. CEC value of reacted bentonite increased by formation of the zeolite minerals under alkaline conditions.

Bentonite, which mostly consists of montmorillonite, is considered as a suitable buffer material for disposal of high-level radioactive wastes in deep geological repository due to its high swelling capacity, low permeability, and strong retention capacity of radionuclide migration. Alkaline and saline solutions originated from degradation of cementitious material and seawater intrusion, respectively, may cause the changes in mineralogical and chemical properties of montmorillonite with various processes such as cation exchange within the interlayer, dissolution of montmorillonite, and precipitation of second minerals. In this study, montmorillonite alteration under alkaline and saline environments and its influences on retention of cesium and iodide by bentonite buffer were investigated. The reactions of bentonite (Bentonil-WRK) with alkaline solutions (0.1 M KOH and NaOH) and simulated saline solution were performed for 7 days in batch experiments at 25°C. After the experiments, reacted bentonite samples were characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Short Wavelength Infrared (SWIR) spectrometry. The concentrations of cesium and iodide dissolved in the solutions were analyzed using an inductively coupled plasma mass spectrometer (ICP–MS). The XRD patterns showed significant decrease in the interlayer space of montmorillonite after the reaction with alkaline solution due to cation exchange and change in hydration status at the interlayer. The retention of cesium and iodide in alkaline and saline solutions were affected by montmorillonite alteration and ion competition. Therefore, the montmorillonite alteration affecting the nuclide retention capacity and long-term stability of bentonite buffer should be considered in the safety assessment of long-term geological disposal performance.

A method to effectively scavenge highly mobile radioiodide into a solid material was developed. Under an anaerobic condition, as copper(II) was strongly associated with bicarbonate (HCO3 −) in solution, malachite quickly formed, and then it was gradually transformed to a compact crystal of CuI (marshite) attracting iodide. The formation of CuI crystal was principally led by the spontaneous Cu-I redox reaction centering around the copper phase over the presence of sulfate (SO4 2−). The transformed CuI crystal was poorly soluble in water. Interestingly, this redox-induced iodide crystallization was rather promoted over the existence of anionic competitors (e.g., HCO3 − and SO4 2−). Unlike the conventional methods, these competing anions positively behaved in our system by supporting that the initial malachite was more apt to be reactive to largely attract highly mobile I−. Under practical environments, such a selective I− uptake and fixation into a crystalline form will be a promising way to effectively remove I− in a great capacity.

This study was evaluated the applicability of the membrane filtration process (Micro Filtration (MF), nanofiltration membranes (NF), reverse osmosis (RO)) on the major radioactive substances, iodine (I-) and cesium (Cs+) using membranes produced in Korea and domestic raw water. Iodine (I-) or cesium (Cs+) in the microfiltration membrane (MF) process could not be expected removal efficiency by eliminating marginally at the combined state with colloidal and turbidity material. At the domestic raw water (lake water, turbidity 1.2 NTU, DOC 1.3 mg/L) conditions, nanofiltration membrane (NF) and reverse osmosis (RO) showed a high removal rate of about 88 ~ 99% for iodine (I-) and cesium (Cs+) and likely to be an alternative process for the removal of radioactive material.

Ag2O를 첨가한 압축 벤토나이트에 대하여 관통 확산법으로 요오드 이온의 이동 특성을 관찰하였다. Ag2O를 첨가하지 않은 압축 벤토나이트와 마찬가지로 Ag2O를 첨가한 압축 벤토나이트에서도 요오드 이온은 확산에 의하여 이동하는데, Ag2O를 첨가한 압축 벤토나이트는 Ag2O를 첨가하지 않은 압축 벤토나이트에 비하여 요오드 이온의 초기 누출 시간이 지연되는 것으로 나타났다. Ag2O를 첨가한 압축 벤토나이트에서 요오드 이온의 초기 누출 시간 지연은 확산 용액으로 순수 요오드 이온 수용액을 사용하였을 때 뿐만 아니라 0.1 M NaCl-요오드 이온 수용액을 사용하였을 때에도 관찰되었다. 또한 Ag2O를 첨가한 압축 벤토나이트의 겉보기 확산 계수는 Ag2O를 첨가하지 않은 압축 벤토나이트의 겉보기 확산 계수보다 낮은 값을 나타내었다. Ag2O를 첨가하지 않은 압축 벤토나이트의 유효 확산 계수는 기존 문헌에 보고된 값 과 거의 일치하는 결과를 얻었으며, Ag2O를 첨가한 압축 벤토나이트에서 요오드 이온의 유효 확산 계수는 Ag2O 첨가에 따라 대체적으로 감소하는 경향을 나타내었다.

원자력시설에서 방사성요오드 제거용으로 사용되는 TEDA 첨착활성탄의 고온공정에서치 메틸요오드의 제거성능을 은이온제올라이트(AgX)와 상호 비교하였다. 3-40 온도범위에서 온도에 따른 메틸요오드의 흡착량 및 탈착후 잔존량을 측정한 결과, 비첨착활성탄의 흡착성능은 온도가 증가함에 따라 급격히 감소하지만 TEDA 첨착활성탄의 흡착성능은 10 부근에서도 AgX-10과 거의 유사한 값을 나타내었고, 탈착후 잔존량은 25 까지도 비첨착활성탄에 비하여 매우 높은 값을 유지하였다. 또한 10 이상의 고온공정에서 AgX 및 TEDA 첨착활성탄을 충전한 고정층 파과특성을 상호 비교한 결과 10 이상에서 AgX-10의 메틸요오드 흡착량 및 잔존량은 TEDA 첨착활성탄에 비하여 평균 30%정도 높은 값을 나타내어 고온에서 더 흡착성능이 우수함을 보여주고 있다. 흡착반응 후 생성된 기체의 성분을 분석한 결과를 토대로 AgX-10 흡착제를 충전한 고정층에서 메틸요오드 제거 메카니즘을 제안하였다.

Adsorption and desorption characteristics of methyl iodide at high temperature conditions up to 250℃ by TEDA-impregnated activated carbon, which is used for radioiodine retention in nuclear facility, was experimentally evaluated. In the range of temperature from 30℃ to 250℃, the adsorption capacity of base activated carbon decreased sharply with increasing temperature but that of TEDA-impregnated activated carbon showed higher value even at high temperature ranges. Especially, the desorption amount of methyl iodide on TEDA-impregnated carbon represented lower value than that on unimpregnated carbon. The breakthrough curves of methyl iodide in the fixed bed packed with base carbon and TEDA-impregnated activated carbon at high temperature were compared. TEDA-impregnated activated carbon would be applicable to adsorption process up to 150℃ for the removal of radioiodine in a nuclear facility.

요오드화수은은 우수한 엑스선 민감도 특성을 가진 광도전체로 비정질 셀레늄을 대체할 수 있는 후보물 질로 많은 연구가 진행되고 있지만 높은 누설전류로 인해 상용화에 많은 한계점을 나타내고 있다. 본 연구 에서는 요오드화수은의 높은 누설전류를 저감하기 위해 요오드화수은에 비해 입자가 작은 이산화규소 및 이산화티타늄을 물리적으로 혼합하여 단위시편을 제작하였으며 제작된 단위시편의 전기적 특성을 비교·분석하였다. 그 결과 혼합한 두 물질 모두 요오드화수은의 높은 누설전류를 저감하는데 효과가 있었으며 요오드화수은-이산화티타늄 혼합물에서는 방사선 민감도 특성이 상당히 높아짐을 확인하였다.

현재 의료용 엑스선 장비는 기존의 아날로그 방식의 필름, 카세트를 대신하여 디지털 방식인 CR, DR 이 널리 사용 되며 그에 관한 연구개발이 활발히 진행되고 있다. 본 연구 에서는 디지털 엑스선 장비의 변환물질로 BiI3(Bismuth tri-iodide)를 적용하여 실험하였으며 기존 선행연구에 비해 만족할만한 결과 값은 얻을 수 없었지만 현재 가장 많이 사용되고 있는 a-Se(Amorphous Selenium)의 단점인 고전압인가와 제작방식의 어려움을 보완할 수 있는 새로운 가 능성을 제시해 주었다. 본 연구에서 사용되어진 변환 물질은 순도 99.99%의 BiI3가 이용되었으며 3cm × 3cm의 크기 와 200um의 두께를 가지는 변환물질 층이 제작되었다. 변환 물질의 상하부에는 Magnetron Sputtering system장비를 이용한 ITO 전극이 형성된다. 형성된 BiI3 엑스선 변환 물질의 특성 평가를 위해 구조적 분석과 전기적 분석이 이루어 졌다. SEM 측정을 통해 제작된 필름의 표면 및 단면적, 구성 성분을 관찰하였고, 전기적 분석을 위해서는 누설전류, 엑스선에 대한 신호량 및 잡음 대 신호비의 관찰이 이루어졌다. 실험 결과 BiI3는 1.6 nA/㎠의 누설전류와 0.629 nC/㎠ 의 신호량을 측정할 수 있었으며, 이렇게 Screen print method로 제작된 엑스선 검출 물질은 PVD방법을 이용해 제작 된 물질과 비슷하거나 더 나은 전기적 특성을 가지고 있었고 이는 제작 방법의 간소화 및 수율을 향상 시킬 수 있어 BiI3도 a-Se를 대체하기 위한 변환물질로 적합하다고 사료된다.