Se sorption onto Ca-type montmorillonite purified from Bentonil-WRK—a new research bentonite introduced by Korea Atomic Energy Research Institute—was examined under ambient conditions (pH 4−9, pe 7−9, I = 0.01 M CaCl2, and T = 25°C). Se(IV) was identified as the oxidation state responsible for weak sorption (Kd < 22 L∙kg−1) by forming surface complexes with edge functional groups of the montmorillonite. Thermodynamic modeling, considering reaction mechanisms of outer-sphere complexation (≡AlOH2 + + HSeO3 − ⇌ ≡AlOH3SeO3, log K = 0.50 ± 0.21), inner-sphere complexation (2≡AlOH + H2SeO3(aq) ⇌ (≡Al)2SeO3 + 2H2O(l), log K = 7.89 ± 0.51), and Ca2+-involved ternary complexation (≡AlOH + Ca2+ + SeO3 2− ⇌ ≡AlOHCaSeO3, log K = 7.69 ± 0.28) between selenite and aluminol sites of montmorillonite, acceptably reproduced the batch sorption data. Outer- and inner-sphere complexes are predominant Se(IV) forms sorbed in acidic (pH ≈ 4) and near-acidic (pH ≈ 6) regions, respectively, whereas ternary complexation accounts for Se(IV) sorption at neutral pHs under the ambient conditions. The experimental and modeling data generally extend a material-specific sorption database of Bentonil-WRK, which is essential for assessing its radionuclide retention performance as a buffer candidate of deep geological disposal system for high-level radioactive waste.

Technetium has been identified as an element of interest for the safety assessment of a deep geological repository for used nuclear fuel. In this study, the sorption of Tc(IV) onto MX-80 bentonite, illite, and shale in ionic strength (I) 0.1–6 mol·kgw−1 (m) Na-Ca-Cl solutions at pHm = 4–9 and limestone at pHm = 5–9 was studied. Tc(IV) sorption on MX-80 increased with pHm from 4 to 6, reached the maximum at pHm = 6–7, and then gradually decreased with pHm from 7 to 9. Tc(IV) sorption on illite gradually increased with pHm from 4 to 7, and then decreased as pHm increased. The sorption properties of Tc(IV) on shale were quite similar to those on illite. Tc(IV) sorption on limestone slightly increased with pHm from 5 to 6 and then seemed to be constant at pHm = 6–9. Tc(IV) sorption on all four solids was independent of ionic strength (0.1–6 m). The 2 site protolysis non-electrostatic surface complexation and cation exchange model successfully simulated the sorption of Tc(IV) onto MX-80 and illite and the optimized values of surface complexation constants were estimated.

Technetium-99 is identified as an element of interest for the safety assessment of a deep geological repository for used nuclear fuel. The sorption behavior of Tc(IV) onto MX-80 and granite in Ca-Na-Cl solutions of varying ionic strength (0.05–1 mol·kgw−1 (m)) and across a pHm range of 4–9 was studied in this paper. Sorption of Tc(IV) was found to be independent of ionic strength in the range of 0.05 to 1 m for both MX-80 and granite. Sorption of Tc(IV) on MX-80 increased with pHm from 4 to 7 and then decreased with pHm from 8 to 9. Sorption of Tc(IV) on granite gradually increased with pHm from 4 to 8 and then became almost constant or slightly decreased with pHm from 8 to 9. A 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model successfully simulated sorption of Tc(IV) on MX-80 and granite. Optimized values of surface complexation constants (log K0) are proposed.

The initial development plans for the six reactor designs, soon after the release of Generation IV International Forum (GIF) TRM in 2002, were characterized by high ambition [1]. Specifically, the sodium-cooled fast reactor (SFR) and very-high temperature reactor (VHTR) gained significant attention and were expected to reach the validation stage by the 2020s, with commercial viability projected for the 2030s. However, these projections have been unrealized because of various factors. The development of reactor designs by the GIF was supposed to be influenced by events such as the 2008 global financial crisis, 2011 Fukushima accident [2, 3], discovery of extensive shale oil reserves in the United States, and overly ambitious technological targets. Consequently, the momentum for VHTR development reduced significantly. In this context, the aims of this study were to compare and analyze the development progress of the six Gen IV reactor designs over the past 20 years, based on the GIF roadmaps published in 2002 and 2014. The primary focus was to examine the prospects for the reactor designs in relation to spent nuclear fuel burning in conjunction with small modular reactor (SMR), including molten salt reactor (MSR), which is expected to have spent nuclear fuel management potential.

This review paper aimed to comprehensively assess the ventilation methods and ventilation rates of livestock sheds, various livestock odor mitigation technologies, and the design flow rate of odor mitigation devices. The most efficient ventilation method for livestock odor control was found to be mechanical ventilation. When livestock odor is at its most severe during summer, ventilation systems are operated at the maximum ventilation rate, which is 5-25 times higher than the ventilation rate in winter. Therefore, the mitigation facilities of livestock odor must be designed while considering the maximum ventilation rate. There is a significant amount of research data on various livestock odor control technologies using various physical, chemical, biological, and complex technologies applied to livestock farms. Biofiltration and photocatalytic oxidation are considered the most promising methods due to their cost-effectiveness and simplicity. Biofiltration is effective for removing hydrophilic odors, but requires improvement for the efficient removal of hydrophobic odors and the control of accumulated excess biomass. The advantages of the photocatalytic oxidation method include its excellent hydrogen sulfide and ammonia removal rates and relatively low ozone emissions. However, it requires technology to reduce nitrous oxide emissions. Investment in installing and operating these odor mitigation technologies is only realistic for large-sized farms. Therefore, it is imperative for small and medium-sized livestock farms to develop odor mitigation technology that is inexpensive and has low installation, operation, and maintenance costs.

The ultimate objective of deep geological repositories is to achieve complete segregation of hazardous radioactive waste from the biosphere. Thus, given the possibility of leaks in the distant future, it is crucial to evaluate the capability of clay minerals to fulfill their promising role as both engineered and natural barriers. Selenium-79, a long-lived fission product originating from uranium- 235, holds significant importance due to its high mobility resulting from the predominant anionic form of selenium. To investigate the retardation behaviors of Se(IV) in clay media by sorption, a series of batch sorption experiments were conducted. The batch samples consisted of Se(IV) ions dissolved in 0.1 M NaCl solutions, along with clay minerals including kaolinite, montmorillonite, and illite-smectite mixed layers. The pH of the samples was also varied, reflecting the shift in the predominant selenium species from selenious acid to selenite ion as the environment can shift from slightly acidic to alkaline conditions. This alteration in pH concurrently promotes the competition of hydroxide ions for Se(IV) sorption on the mineral surface as the pH increases and impedes the selective attachment of selenium. The acquired experimental data were fitted through Langmuir and Freundlich sorption isotherms. From the Freundlich fit data, the distribution coefficient values of Se(IV) for kaolinite, montmorillonite, and illite-smectite mixed layer were derived, which exhibited a clear decrease from 91, 110, 62 L/kg at a pH of 3.2 to 16, 6.3, 12 L/kg at a pH of 7.5, respectively. These values derived over the pH range provide quantitative guidance essential for the safety assessment of clay mineral barriers, contributing to a more informed site selection process for deep geological repositories.

The Colloid Formation and Migration (CFM) international joint research initiative continues as a part of the GTS’s Radionuclide Retardation Programme, which has been in progress since 1984. This project focuses on examining the formation of colloids from a bentonite-engineered barrier system and exploring how these colloids impact the migration of radionuclides in fractured host rock when subjected to advective flow. Phase 1 of the project was launched in 2004 and concluded in early 2008, focusing on preliminary studies related to in-situ boundary conditions, predicting models, and supplementary lab works. Following that, Phase 2 spanned from 2008 to 2013 and aimed at fortifying the field setup by adding three new monitoring boreholes and suitable instrumentation in both the boreholes and tunnel. This phase also tested the system’s resilience while mapping the flow domain. Phase 3 kicked off in January 2014 and extended until December 2018. During this period, the Long-term In-situ Test (LIT) was introduced in May 2014, featuring a set of compacted bentonite rings laced with radionuclide tracers. These were placed in a borehole to serve as a colloid and radionuclide source. CFM Phase 4 initiative commenced in January 2019, marking the successful deployment of the i-BET (In-situ Bentonite Erosion Test). This project component involves placing approximately 50 kg of compacted bentonite in a natural water-conducting shear zone. Korea Atomic Energy Research Institute (KAERI) joined CFM in 2008 to examine the behavior of colloid generation and migration with radionuclides in the Underground Research Laboratory. The fourth phase of the CFM project was also scheduled to include a post-mortem evaluation of the LIT and additional tracer experiments in the well-mapped MI shear zone. This study aims to provide an interim update on the ongoing i-BET, a key component of Phase 4 of the CFM project. We will also discuss the current status of the post-mortem analysis for the LIT experiment. In addition, we will outline plans for the forthcoming Phase VI of the project. These plans will continue to advance our understanding of radionuclide migration and the influence of bentonite-based disposal systems.

Th(IV) is a stable actinide that can act as a chemical analogue of U(IV) and Pu(IV), which are important radionuclides in safety assessments of deep geological repositories (DGR). Therefore, to understand the geochemical behaviour of U(IV) and Pu(IV), batch sorption of Th(IV) onto crystalline rocks were performed in oxidising conditions. The distribution coefficients (Kd) of Th(IV) were of particular interest. Gyeongju fresh groundwater (GF) and Gyeongju brackish groundwater (GB) were obtained at the Gyeongju Low and Intermediate Level Radioactive Waste (LILW) Disposal Facility. Crystalline granite (gr) and biotite gneiss (bg) were collected in Gyeongju and Gwacheon respectively and were grounded to a particle size smaller than 150 μm. Sorption samples were continuously shaken for 7 days under 200 rpm at 25°C. The liquid-to-solid ratio (V/m) was 200 L·kg-1. Th(IV) concentrations of the sorption samples were determined by UV-Vis-NIR absorption colorimetry from the formation of Th(IV)-arsenazo III complexes. Although the method allowed the initial Th(IV) concentrations to be determined, the final Th(IV) concentrations fell below the limit of detection (LOD), 6.27×10-9 mol·L-1. Taking the LOD as the final concentrations, conservative Kd were calculated to be 4,410 L·kg-1 for GF-gr and GF-bg, and 7,830 L·kg-1 for GB-gr and GB-bg. The result indicates a strong sorption affinity of Th(IV) onto granite and biotite gneiss within Gyeongju groundwater, suggesting a similar behaviour for U(IV) and Pu(IV). Furthermore, comparison of the conservative Kd obtained from the experiment were compared with existing Kd values of Th(IV). Such analysis and comparison of Th(IV) Kd in various types of groundwater could help locate the optimal site for a DGR in South Korea.

The stabilization technology for the damaged spent fuel is being developed to process the damaged fuel into sound pellet suitable for dry re-fabrication. It requires several treatments including oxidative decladding followed by reduction treatment for oxidized powder closely related to the quality of oxidized powders for pellet fabrication. For the development of operating condition for the reduction treatment, in this study, we evaluated the effect of air-cylinder based vertical shaking previously applied to oxidative decladding on powder reduction. For U3O8 of 50-100 g, the reduction test were applied with and without vertical shaking at 700°C under reduction atmosphere (Ar + 4%H2) and the concentration of hydrogen in effluent was measured to evaluate the reduction reaction. It was found that the vertical shaking system has allowed the reaction time of 50 g and 100 g U3O8 reduced by 33% compared to the test in static mode. Based on XRD analysis, the better crystallinity of the products was also achieved.

Technetium (Tc) is a long-lived radioactive isotope, which exists as TcO4 - with high solubility under oxidative condition. The solubility of Tc is fundamental to assess the safety of radioactive waste repository in the case of a leakage of radioactive wastes. Cellulosic materials (paper, wood, cotton, etc.) contaminated by radionuclides are disposed of in low-level and intermediate-level radioactive waste repositories. Cellulose can be decomposed under anaerobic and alkaline conditions when cement pore water is saturated, and then isosaccharinic acid (ISA) is generated as a degradation product of cellulose. ISA forms complexations with radionuclides in solution and affects the solubilities of radionuclides. Therefore, the effect of ISA should be accurately evaluated to predict and assess the mobility of radionuclides in repository environments. In this study, batch tests were conducted to confirm the effect of ISA on the solubility of Rhenium(IV) Oxide. Herein, rhenium was used as a non-radioactive analog of Tc due to their similar chemical properties. Deionized water (DIW) and 0.1 M NaOH solution in pH 12.5 were used as background solutions, and ISA concentration was varied to 1~20 mM using Ca(ISA)2 and NaISA, respectively. The batch tests were conducted under both aerobic and anaerobic conditions. The whole batch tests under anaerobic conditions were performed in the glove box using oxygen purged DIW with a high purity nitrogen gas (99.9%) and low oxygen concentration (< 0.5 ppm). As a result, the rhenium concentration decreases as more ISA is dissolved in the solution, which shows the contrary effect of ISA on the solubility of other metals and radionuclides (e.g., Co, Th, Fe, Ni, etc.). It is assumed that the reducing capacity of ISA decreases the rhenium dissolution in the solution. Additional characterization of the oxidation state of rhenium oxide and the mechanism will be tested and presented.

A strain of Alexandrium species was established by isolating cells from Jangmok Bay, Korea. Its morphology and molecular phylogeny based on LSU rRNA gene sequences were examined. In addition, growth responses of this Alexandrium species to changes in temperature, salinity, and nutrient concentrations were investigated. This Alexandrium species from Jangmok Bay had a ventral pore on the 1′, which was morphologically consistent with previously described Alexandrium tamarense and A. catenella. Phylogenetic analyses revealed that this isolate was assigned to A. pacificum (Group IV) within A. tamarense species complex. In growth experiments, relatively high growth rates and cell densities of A. pacificum (Group IV) were observed at 15°C and 20°C. This species also grew under a wide range of salinity. This indicates that this Korean isolate of A. pacificum (Group IV) is a stenothermic and euryhaline species. In growth responses to changes in nutrient levels, enhanced growth rates and cell densities of A. pacificum (Group IV) were observed with additions of nitrate and phosphate. In particular, rapid uptakes of phosphate by A. pacificum (Group IV) were observed in experimental treatments, indicating that the increase in phosphate concentration could stimulate the growth of A. pacificum (Group IV).

The sorption behavior of Se(IV) on montmorillonite clay, a promising buffer and backfill material, was investigated in the presence of aquatic fulvic acid. Selenium-79 is one of the major radioactive nuclides which are long-lived and highly mobile in subsurface environments. Moreover, it is highly toxic even in small amounts, so the selenium quantity in soil and groundwater should be assessed. Although natural organic matters such as humic and fulvic acids are present in the environment, the influence of natural organic matters on Se(IV) migration has not yet been extensively studied. The batch sorption experiments were performed under oxic conditions. Suwannee River III standard aquatic fulvic acid (International Humic Substances Society) was used to build an organicrich environment. The N2 – BET surface area of the montmorillonite (Clay Minerals Society) was 97 ± 5 m2·g−1. The montmorillonite suspensions with/without fulvic acid were equilibrated with air before adding Na2SeO3. The solid-to-liquid ratio was 5 g·L−1, the ionic medium was 0.1 M NaCl, fulvic acid concentration was 50 mg·L−1, and the final pH was 3. The horizontal vial roller was used to prevent the clay from sinking. After 7 days of sorption at room temperature, the suspensions were centrifuged at 10,600 g for 15 min and filtered through 0.2 μm PTFE filters. The colloidal fulvic selenide and free Se(IV) concentrations were entirely measured by inductively coupled plasma–mass spectrometry (ICP-MS). The sorption results were fitted with Langmuir and Freundlich models. At concentrations lower than 20 μM, the distribution coefficients (Kd) were 50 ± 9 L·kg−1 without fulvic acid, and 36 ± 5 L·kg−1 with 50 mg·L−1 fulvic acid. For the concentrations between 20 and 100 μM, the Kd values without and with fulvic acid were 16 ± 7 L·kg−1 and 10 ± 1 L·kg−1, respectively. As a result, it turned out that fulvic acid interferes with the sorption of Se(IV) on montmorillonite in competition with the selenite anion. This indicates that such organic matter may facilitate the migration of selenium in deep geological groundwaters.

99Tc is a long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Migration of Tc from a waste repository may be prevented by immobilizing Tc(IV) in durable glass forms. Thus, efficient incorporation and high retention of Tc by glasses is very important for radioactive waste management and environmental remediation. Tc(IV) oxidation to higly volatile Tc(VII) (TcO4 −) at glass vitrification temperatures results in poor Tc retention in the final waste glass. Retention of Tc in the glass is generally improved by reducing conditions since Tc(IV) is not volatile. However, experiments with Tc-magnetite under high temperature and oxic conditions showed re-oxidation of Tc(IV) to volatile pertechnetate. To understand this phenomenon, we employed ab initio molecular dynamics simulations to study structural and electronic properties of Tc-incorporation in magnetite. The study provides the ramification of high temperature on Tc mobilization and changes of Tc retention in magnetite. Theory predictions also indicated enhanced Tc retention in the presence of 1st row transition metal dopants in Tc-incorporated magnetite that was confirmed by experiments. Furthermore, the overwhelming concentration of Cr(VI) co-mingled with Tc(VII) within the secondary waste form where Cr(VI) is more readily reduced than Tc(VII) by reduction potential metrics. Experiments with Tc-magnetite under high temperature and oxic conditions showed re-oxidation of Tc(IV) to volatile pertechnetate. Experiments also showed that magnetite transforms to maghematite resulting in disproportionation and re-oxidation of Tc. This transformation can be suppressed through incorporation of trace elements such as Co, Ni, Zn into magnetite forming spinel. In this talk, I will present results from ab initio molecular dynamics simulations and experiments on the structural and electronic properties of Tc and/or Cr incorporation in magnetite. I will also discuss the temperature effect on Tc/Cr mobilization and changes of Tc/Cr retention in magnetite. In addition, I will discuss the effect of Tc/Cr concentration and 1st row transition metal dopants on their incorporation in magnetite.

Mechanism and kinetics of Rhenium complexes as a surrogate of Technetium-99 (99Tc) is worthy of study from radioactive waste safe disposal perspective. Re(IV)-EDTA was synthesized via the reduction of Re(VII) with Sn(II) in the presence of Ethylenediaminetetracetic acid (EDTA). The Re(IV)-EDTA was then degraded by H2O2 (7–30%) at pH of 3–11 in ionic strength I = 0–2 M solution. The Re- EDTA was observed to degrade more rapidly at pH of ≤ 3–4 than one of ≥ 10–11 and remained stable at pH = 7–9. At a low acidic pH, the complex degradation process was facilitated by protonation and corresponded to the exponential model (y = k. e–nt). In contrast, at an alkaline pH, the degradation was facilitated OH– complexation with Re(IV) and corresponded to a linear model (y = –mt + C). Complex degradation followed the zero-order rate kinetics for the H+ and Re-EDTA parameters, apart from a pH of 3, for which degradation was a better fit to first order kinetics. A higher Re(IV)-EDTA stability at a pH of 7–9 demonstrated that Re(IV)-EDTA (or 99Tc(IV)-EDTA) tends to be more persistent in natural environmental conditions.

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.