In this study, gold nanoparticles (AuNPs) were synthesised using green chemistry to decorate multi-walled carbon nanotubes (MWCNTs) made from walnut shells transmission electron microscopy, field-emission scanning electron microscopy (FESEM), atomic force microscopy and fourier transforms infrared spectroscopy were used to diagnose MWCNTs and AuNPs. MWCNT-COOAu, MWCNT-COO and MWCNT-Au were diagnosed by Raman, energy dispersive X-ray analysis and FESEM. The effect of AuNPs, MWCNT-COO, MWCNT-COOAu and MWCNT-Au on pure and serum alkaline phosphatase (ALP) enzyme activity was studied in vitro using the enzyme-substrate 4-nitrophenyl disodium orthophosphate. For pure enzymes, Vmax slightly increased as the concentration of MWCNT-Au, MWCNT-COOAu and MWCNTCOO increased, whereas the Vmax values decreased as the concentration of AuNPs increased. The inhibition type for all NPs varied. For serum ALP enzyme, the Vmax values for Au-based NPs decreased as the concentration of NPs increased. The Vmax values exceeded the standard value at the concentrations of 25, 50 and 75 ppm for MWCNT-Au and MWCNT-COOAu, whereas the Vmax values increased over the standard value for all concentrations of AuNPs.

Mobility of radionuclides (RNs) in natural water systems can be increased by complex formation with organic materials. In alkaline cement pore-water conditions, cellulose materials in radwastes such as woods and papers are degraded fast to small organic materials. As a major cellulose degradation product, isosaccharinate (ISA) has been paid attention recently due to its effect on facilitating RNs migration. ISA contains a carboxyl and four hydroxyl functional groups, which cooperatively interact to form chelating bonds with positively charged radionuclides. In our previous study, we determined thermodynamic formation constants, reaction enthalpy and entropy of trivalent americium complexes with ISA, Am(ISA)n (3-n)+ (n=1, 2), in weak acidic condition by conducting temperature-dependent UVVis absorption spectroscopy. Based on those thermodynamic constants along with the experimental results from time-resolved laser induced fluorescence spectroscopy and DFT calculations, we suggested two different chelating-modes of ISA on Am(III). It is more relevant to study Am(III)-ISA complexation under alkaline conditions around pH 12.5, which correspond to the pore-water condition of calciumsilicate- hydrate. Under the alkaline conditions, deprotonated hydroxyl groups of ISA can form more strong interactions with Am. Aquatic hydroxide group can also act as a ligand to form ternary Am(III) -ISA-OH complexes. In this study, absorption spectra of Am-ISA systems were monitored with two variations: first, pH variation (5.5–13) in the presence of constant 30 mM ISA, and second, ISA concentration variation (20 μM – 30 mM) at constant pH of 12.5. As increasing the pH at constant 30 mM ISA, absorption spectra of Am(ISA)2 + were red-shifted from 506.3 to 509.5 nm. The samples showed stable absorption spectra over 30 days. On the other hand, samples with lower ISA concentrations below 10 mM at pH 12.5, showed gradual decrease in the absorbance as sample aging time. By examining filtrates after ultrafiltration (1 kDa), we confirmed that aqueous Am(III)-ISA complexes were formed in the presence of 30 mM ISA at pH 12.5, while colloidal particles and precipitations were formed in the conditions of ISA concentrations lower than 10 mM. In this presentation, we will discuss about probable ternary complex forms of Am(III)-ISA-OH, colloidal forms, and solubility of Am(III) as a function of ISA concentration under alkaline conditions. Absorption and luminescence spectroscopic properties of the Am(III)-ISA-OH ternary system will also be presented.

In the deep geological repository, a considerable quantity of cementitious materials is generally used for structural stability of subcomponents such as grout and concrete plug of disposition tunnel. Strong alkaline leachates (pH>13) are produced after cement is dissolved by groundwater inflow from bedrock. When the leachates are transported to bentonite porewater (e.g. buffer and backfill) and thereby water exchange occurs, the physical properties of bentonite such as swelling capacity and hydraulic conductivity are changed, which eventually affects the safety function and long-term stability of engineered barrier system (EBS). Thus, in this paper, we reviewed the performance assessment methodology for cement-bentonite interaction in the operating license application for the Finnish deep geological repository, and suggested what to prepare for the analysis on the domestic disposal facility. In Finland, thermal-hydraulic-chemical analysis for dissolution of montmorillonite by alkaline leachates resulting from cement degradation during the saturation of bentonite was carried out using PRECIP code. From this analysis, it was confirmed that effect on pH was considered to be more significant than that on temperature and bentonite saturation. As a result of this analysis, it was predicted that all primary minerals (including montmorillonite, quartz, and calcite) were dissolved and some secondary minerals (e.g. chalcedony and celadonite) was precipitated by alkaline cement leachates transported to the bentonite. In addition, it was shown that silica was preferentially released while the montmorillonite was dissolved, thus cementation of the bentonite was occurred. Through this phenomenon, the swelling capacity of bentonite is reduced and the hydraulic conductivity of bentonite is increased, which have a significant impact on the performance of the buffer and backfill. Considering this, study on spreading of alkaline leachates, which is a condition for dissolution of montmorillonite, is necessary for the performance assessment of the domestic deep geological repository. However, this requires the site-specific data for the following in the disposal site: (a) distribution in fractured bedrock and pore structure (e.g. porosity, pore size distribution and pore morphology) in the bedrock, (b) hydraulic gradient and salinity concentration of groundwater, and (c) flux and velocity of groundwater. Results of this study is considered to be directly utilized to the conceptual design and performance assessment of the deep geological repository in Korea, provided that additional data on microbiological properties of groundwater are obtained for the site selected.

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.

The volatilization of alkali ions in (K,Na)NbO3 (KNN) ceramics was inhibited by doping them with alkaline earth metal ions. In addition, the grain growth behavior changed significantly as the sintering duration (ts) increased. At 1,100 °C, the volatilization of alkali ions in KNN ceramics was more suppressed when doped with alkaline earth metal ions with smaller ionic size. A Ca2+-doped KNN specimen with the least alkali ion volatilization exhibited a microstructure in which grain growth was completely suppressed, even under long-term sintering for ts = 30 h. The grain growth in Sr2+-doped and Ba2+-doped KNN specimens was suppressed until ts = 10 h. However, at ts = 30 h, a heterogeneous microstructure with abnormal grains and small-sized matrix grains was observed. The size and number of abnormal grains and size distribution of matrix grains were considerably different between the Sr2+-doped and Ba2+-doped specimens. This microstructural diversity in KNN ceramics could be explained in terms of the crystal growth driving force required for two-dimensional nucleation, which was directly related to the number of vacancies in the material.

Environmental issues such as global warming due to fossil fuel use are now major worldwide concerns, and interest in renewable and clean energy is growing. Of the various types of renewable energy, green hydrogen energy has recently attracted attention because of its eco-friendly and high-energy density. Electrochemical water splitting is considered a pollution-free means of producing clean hydrogen and oxygen and in large quantities. The development of non-noble electrocatalysts with low cost and high performance in water splitting has also attracted considerable attention. In this study, we successfully synthesized a NiCo2O4/NF electrode for an oxygen evolution reaction in alkaline water splitting using a hydrothermal method, which was followed by post-heat treatment. The effects of heat treatment on the electrochemical performance of the electrodes were evaluated under different heat-treatment conditions. The optimized NCO/NF-300 electrode showed an overpotential of 416 mV at a high current density of 50 mA/cm2 and a low Tafel slope (49.06 mV dec-1). It also showed excellent stability (due to the large surface area) and the lowest charge transfer resistance (12.59 Ω). The results suggested that our noble-metal free electrodes have great potential for use in developing alkaline electrolysis systems.

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.