Concrete is the primary building material for nuclear facilities, making it one of the most common forms of radioactive waste generated when decommissioning a nuclear facility. Of the total waste generated at the Connecticut Yankee and Maine Yankee nuclear power plants in the United States, concrete waste accounts for 83.5% of the total for Connecticut Yankee and 52% for Maine Yankee. In order to dispose of the low- to medium-level radioactive concrete waste generated during the decommissioning of nuclear power plants, it is necessary to analyze the radioactivity concentration of gamma nuclides such as Co-58, Co-60, Cs-137, and Ce-144. Gamma-ray spectroscopy is commonly used method to measure the radioactivity concentration of gamma nuclides in the radioactive waste; however, due to the nature of gamma detectors, gamma rays from sequentially decaying nuclides such as Co-60 or Y-88 are subject to True Coincidence Summing (TCS). TCS reduces the Full Energy Peak Efficiency (FEPE) of specific gamma ray and it can cause underestimation of radioactivity concentration. Therefor the TCS effect must be compensated for in order to accurately assess the radioactivity of the sample. In addition, samples with high density and large volume will experience a certain level of self-shielding effect of gamma rays, so this must also be compensated for. The Radioactive Waste Chemical Analysis Center at the Korea Atomic Energy Research Institute performs nuclide analysis for the final disposal of low- and intermediate-level concrete waste. Since a large number of samples must be analyzed within the facility, the analytical method must simultaneously satisfy accuracy and speed. In this study, we report on the results of evaluating the accuracy of the radioactivity concentration correction by applying an efficiency transfer method that appears to satisfy these requirements to concrete standard reference material.

The inorganic scintillator used in gamma spectroscopy must have good efficiency in converting the kinetic energy of charged particles into light as well as high light output and high light detection efficiency. Accordingly, various studies have been conducted to enhance the net-efficiency. One way to improve the light yield has been studied by coating scintillators with various nanoparticles, so that the scintillation light can undergo resonance on surface between scintillators and nanoparticles resulting in higher light yield. In this study, an inorganic scintillator coated with CsPbBr3 perovskite nanocrystals using dip coating technique was proposed to improve scintillation light yield. The experiment was carried out by measuring scintillation light output, as the result of interaction between inorganic scintillator coated with CsPbBr3 perovskite nanocrystals and gamma-ray emitted from Cs-137 gamma source. The experimental results show that the channel corresponding to 662 keV full energy peak in the Cs-137 spectrum shifted to the right by 14.37%. Further study will be conducted to investigate the detailed relationships between the scintillation light yield and the characteristics of coated perovskite nanoparticles, such as diameter of nanoparticles, coated area ratio and width of coated region.

Raman characteristics of various minerals constituting natural rocks collected from uranium deposits in Okcheon metamorphic zone in Korea are presented. Micro-Raman spectra were measured using a confocal Raman microscope (Renishaw in Via Basis). The focal length of the spectrometer was 250 mm, and a 1800 lines/mm grating was installed. The outlet of the spectrometer was equipped with a CCD (1,024256 pixel) operating at -70°C. Three objective lenses were installed, and each magnification was 10, 50, and 100 times. The diameter of the laser beam passing through the objective lens and incident on the sample surface was approximately 2 m. The laser beam power at 532 nm was 1.6 mW on the sample surface. Raman signal scattered backward from the sample surface was transmitted to the spectrometer through the same objective lens. To accurately determine the Raman peak position of the sample, a Raman peak at 520.5 cm-1 measured on a silicon wafer was used as a reference position. Since quartz, calcite, and muscovite minerals are widely distributed throughout the rock, it is easy to observe with an optical microscope, so there is no difficulty in measuring the Raman spectrum. However, it is difficult to identify the uraninite scattered in micrometer sizes only with a Raman microscope. In this case, the location of uraninite was first confirmed using SEM-EDS, and then the sample was transferred to the Raman microscope to measure the Raman spectrum. In particular, a qualitative analysis of the oxidation and lattice conditions of natural uraninite was attempted by comparing the Raman properties of a micrometer-sized natural uraninite and a laboratory-synthesized UO2 pellet. Significantly different T2g/2LO Raman intensity ratio was observed in the two samples, which indicates that there are defects in the lattice structure of natural uraninite. In addition, no uranyl mineral phases were observed due to the deterioration of natural uraninite. This result suggests that the uranium deposit is maintained in a reduced state. Rutile is also scattered in micrometer-sizes, similar to uraninite. The Raman spectrum of rutile is similar in shape to that of uraninite, making them confused. The Raman spectral differences between these two minerals were compared in detail.

Fulvic acid, a humic substance with unique properties, has sparked interest due to its potential applications in the treatment of allergic diseases, Alzheimer's disease, and as a microplastic adsorbent. However, conventional extraction methods produce insufficient quantities for commercial use, which has prompted research to enhance fulvic acid production. In this study, we investigated the impact of Saccharomyces cerevisiae fermentation on the yield and spectral characteristics of fulvic acid extracted from white peat. Fulvic acid was extracted from both S. cerevisiae-treated and untreated white peats using acid precipitation. The yield of fulvic acid from the S. cerevisiae treated group reached its highest at 3.5 % after 72 hr of fermentation, which was significantly higher than the untreated group (1.1 %). Fourier Transform Infrared (FTIR) analysis revealed similarities in functional groups and characteristic absorption bands between the treated and untreated fulvic acid samples. These findings suggest that S. cerevisiae fermentation can increase the yield of fulvic acid extracted from white peat, providing a promising approach for enhancing the commercial viability of fulvic acid production.

Some of the metal waste generated from KEPCO NF is being disposed of in the form of ingots. An ingot is a metal that is melted once and then poured into a mold to harden, and it is characterized by a uniform distribution of radioactive material. When measuring the uranium radioactivity in metal ingot with HPGe detector, 185.7 keV of U-235 is used typically because most gamma rays emitted at U-235 are distributed in low-energy regions below 200 keV. To analyze radioactivity concentration of U-235 with HPGe detector more accurately, self-attenuation due to geometrical differences between the calibration source and the sample must be corrected. In this study, the MCNP code was used to simulate the HPGe gamma spectroscopy system, and various processes were performed to prove the correlation with the actual values. First an metal ingottype standard source was manufactured for efficiency calibration, and the GEB coefficient was derived using Origin program. And through the comparison of actual measurements and simulations, the thickness of the detector’s dead layers were defined in all directions of Ge crystal. Additionally instead of making an metal ingot-type standard source every time, we analyzed the measurement tendency between commercially available HPGe calibration source (Marinelli beaker type) and the sample (metal ingot type), and derived the correction factor for geometry differences. Lastly the correction factor was taken into consideration when obtaining the uranium radioactivity concentration in the metal ingot with HPGe gamma spectroscopy. In conclusion, the U-235 radioactivity in metal ingot was underestimated about 25% of content due to the self-attenuation. Therefore it is reasonable to reflect this correction factor in the calculation of U-235 radioactivity concentration.

Neptunium (Np) is one of the daughter elements included in the decay chain of Pu. The quantitative analysis of Np isotopes is required for radioactive waste characterization, research on actinide chemistry, etc. Np-237 has a long half-life (2.144 million years), but its daughter Pa-233 has a relatively short half-life (26.975 days). For this reason, after a sufficient time elapses following the chemical preparation process of the analyte, the two nuclides are in radiation equilibrium in the sample. Np-237 emits alpha-rays while Pa-233 emits beta-rays. Both nuclides also emit gamma- and X-rays. In this study, alpha-rays were measured using liquid scintillation counting (LSC) method and alpha spectrometry. Gamma-spectrometry with a HPGe detector was used for the analysis of gammaand X-rays. In addition, we compared the radiometric results with quantitative analysis of Np using UV-Vis absorption spectrometry. The LSC method and the HPGe gamma-spectroscopy do not require extensive sample preparation procedures. Alpha spectroscopy requires a standard material spiking, separation by coprecipitation, and disk-type sample preparation procedure to obtain measurement efficiency and recovery factor. A reference material sample with a concentration of 5.8 mM was analyzed by the four analysis methods, and all of the measured results agreed well within a difference level of 4%.

Plastic scintillators can be used to find radioactive sources for portal monitoring due to their advantages such as faster decay time, non-hygroscopicity, relatively low manufacturing cost, robustness, and easy processing. However, plastic scintillators have too low density and effective atomic number, and they are not appropriate to be used to identify radionuclides directly. In this study, we devise the radiation sensor using a plastic scintillator with holes filled with bismuth nanoparticles to make up for the limitations of plastic materials. We use MCNP (Monte Carlo N-particle) simulating program to confirm the performance of bismuth nanoparticles in the plastic scintillators. The photoelectric peak is found in the bismuth-loaded plastic scintillator by subtracting the energy spectrum from that of the standard plastic scintillator. The height and diameter of the simulated plastic scintillator are 3 and 5 cm, respectively, and it has 19 holes whose depth and diameter are 2.5 and 0.2 cm, respectively. As a gamma-ray source, Cs-137 which emits 662 keV energy is used. The clear energy peak is observed in the subtracted spectrum, the full width at half maximum (FWHM) and the energy resolution are calculated to evaluate the performance of the proposed radiation sensor. The FWHM of the peak and the energy resolution are 61.18 keV and 9.242% at 662 keV, respectively.

Dose-rate monitoring instruments are indispensable to protect workers from the potential risk of radiation exposure, and are commonly calibrated in terms of the ambient dose equivalent (H*(10)), an operational quantity that is widely used for area monitoring. Plastic scintillation detectors are ideal equipment for dosimetry because of their advantages of low cost and tissue equivalence. However, these detectors are rarely used owing to the characteristics caused by low-atomic-number elements, such as low interaction coefficients and poor gamma-ray spectroscopy. In this study, we calculated the G(E) function to utilize a plastic scintillation detector in spectroscopic dosimetry applications. Numerous spectra with arbitrary energies of gamma rays and their H*(10) were calculated using Monte Carlo simulations and were used to obtain the G(E) function. We acquired three different types of G(E) functions using the least-square and first-order methods. The performances of the G(E) functions were compared with one another, including the conventional total counting method. The performance was evaluated using 133Ba, 137Cs, 152Eu, and 60Co radioisotopes in terms of the mean absolute percentage error between the predicted and true H*(10) values. In addition, we confirmed that the dose-rate prediction errors were within acceptable uncertainty ranges and that the energy responses to 137Cs of the G(E) function satisfied the criteria recommended by the International Commission.

During electrorefining, fission products, such as Sr and Cs, accumulate in a eutectic LiCl-KCl molten salt and degrade the efficiency of the separation process by generating high heat and decreasing uranium capture. Thus, the removal of the fission products from the molten salt bath is essential for reusing the bath, thereby reducing the additional nuclear waste. While many studies focus on techniques for selective separation of fission products, there are few studies on processing monitoring of those techniques. In-situ monitoring can be used to evaluate separation techniques and determine the integrity of the bath. In this study, laser-induced breakdown spectroscopy (LIBS) was selected as the monitoring technique to measure concentrations of Sr and Cs in 550°C LiCl-KCl molten salt. A laser spectroscopic setup for analyzing high-temperature molten salts in an inert atmosphere was established by coupling an optical path with a glove box. An air blower was installed between the sample and lenses to avoid liquid splashes on surrounding optical products caused by laser-liquid interaction. Before LIBS measurements, experimental parameters such as laser pulse energy, delay time, and gate width were optimized for each element to get the highest signal-to-noise ratio of characteristic elemental peaks. LIBS spectra were recorded with the optimized conditions from LiCl-KCl samples, including individual elements in a wide concentration range. Then, the limit of detections (LODs) for Sr and Cs were calculated using calibration curves, which have high linearity with low errors. In addition to the univariate analysis, partial least-squares regression (PLSR) was employed on the data plots to obtain calibration models for better quantitative analysis. The developed models show high performances with the regression coefficient R2 close to one and root-mean-square error close to zero. After the individual element analysis, the same process was performed on samples where Sr and Cs were dissolved in molten salt simultaneously. The results also show low-ppm LODs and an excellent fitted regression model. This study illustrates the feasibility of applying LIBS to process monitoring in pyroprocessing to minimize nuclear waste. Furthermore, this high-sensitive spectroscopic system is expected to be used for coolant monitoring in advanced reactors such as molten salt reactors.

One of the promising candidates for heat transfer fluid is molten chloride salts. They have been studied in various fields such as the electrolyte of pyroprocessing, the molten salt reactor coolant, and the energy storage system media. Main considerations for utilizing molten chloride salts are the compatibility of salts with structural materials. The corrosion behavior of structural materials in molten chloride salts must be understood to identify suitable materials against the corrosive environment. In this study, the corrosion behavior of a candidate structural material, Hastelloy N, in molten LiCl- KCl salt at 500°C were investigated by the electrochemical impedance spectroscopy (EIS) method. The sheet type of Hastelloy N was utilized as the working electrode in LiCl-KCl to measure the EIS data for 100 hours with 5 hours of time intervals. The EIS data were measured in the frequency range from 104 Hz to 10-2 Hz with the AC signal (amplitude = 20 mV) at open circuit potential. The capacitance semicircle observed in Nyquist plots for all periods indicates that charge-transfer controlled reactions occur. As the immersion time progresses, the radius of the semicircle in Nyquist plots and the impedance and phase angle in Bode plots decrease. These behaviors suggest a decreasing reaction resistance and the corrosion reactions are accelerated with the immersion time. The EIS data were fitted using the equivalent circuit to achieve quantitative results. Two capacitor-resistor components were considered due to the overlapped shape of two valleys in phase angle. The depressed shape of the semicircle in Nyquist plots led to the use of the constant phase element(Q) instead of the capacitor. Therefore, R(Q(R(QR))) circuit was selected to fit the EIS data. Fitting results show that the charge transfer resistance decreases dramatically within 1 day and then converges. The film resistance shows no clear trends, but the increase of the film admittance value indicates the decreased film thickness. Consequently, the film appears to exist like the oxide layer but it does not act as a protective layer. The real-time EIS data were measured in molten salt and provides the corrosion behavior over time. The corrosion mitigation strategy should consider that the corrosion of Hastelloy N accelerates over time and its intrinsic film cannot act as the protective layer. The next steps of this study are to evaluate other candidate structural materials and to demonstrate the presence of the film.

Molten salt reactors and pyroprocessing are widely considered for various nuclear applications. The main challenges for monitoring these systems are high temperature and strong radiation. Two harsh environments make the monitoring system needs to measure nuclides at a long distance with sufficient resolution for discriminating many different elements simultaneously. Among available methodologies, laser-induced breakdown spectroscopy (LIBS) has been the most studied. The LIBS method can provide the required stand-off and desired multi-elemental measurable ability. However, the change of the level for molten salts induces uncertainty in measuring the concentration of the nuclides for LIBS analysis. The spectra could change by focusing points due to the different laser fluence and plasma shape. In this study, to prepare for such uncertainties, we evaluated a LIBS monitoring system with machine learning technology. While the machine learning technology cannot use academic knowledge of the atomic spectrum, this technique finds the new variable as a vector from any data including the noise, target spectrum, standard deviation, etc. Herein, the partial least squares (PLS) and artificial neural network (ANN) were studied because these methods represent linear and nonlinear machine learning methods respectively. The Sr (580–7200 ppm) and Mo (480–4700 ppm) as fission products were investigated for constructing the prediction model. For acquiring the data, the experiments were conducted at 550°C in LiCl-KCl using a glassy carbon crucible. The LIBS technique was used for accumulating spectra data. In these works, we successfully obtained a reasonable prediction model and compared each other. The high linearities of the prediction model were recorded. The R2 values are over 0.98. In addition, the root means square of the calibration and cross-validation were used for evaluating the prediction model quantitatively.

Complexation of actinides and lanthanides with carboxylic organic ligands is known to facilitate migration of radionuclides from deep geological disposal systems of spent nuclear fuel. In order to examine the ligand-dependent structures of trivalent actinides and lanthanides, a series of Eu(III)-aliphatic dicarboxylate compounds, Eu2(oxalate)3(H2O)6, Eu2(malonate)3(H2O)6, and Eu2(succinate)3(H2O)2, were synthesized and characterized by using X-ray crystallography and time-resolved laser fluorescence spectroscopy. Powder X-ray diffraction results captured the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence of these solid compounds, especially on the hypersensitive peak, indicates a low site symmetry of these solid compounds. Luminescence lifetimes of the compounds were measured to be increased, which is ascribed to the displacement of water molecules in the innersphere of Eu center upon bindings of the organic ligands. The numbers of remaining bound water molecules estimated from the increased luminescence lifetimes were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that oxalate ligands promote the sensitized luminescence of Eu(III), especially in the UV region. In the case of malonate and succinate ligands, charge transfer occurs in the opposite direction from Eu(III) to the ligands under UV excitation, resulting in weaker luminescence.

Gamma-ray spectroscopy, which is an appropriate method to identify and quantify radionuclides, is widely utilized in radiological leakage monitoring of nuclear facilities, assay of radioactive wastes, and decontamination evaluation of post-processing such as decommissioning and remediation. For example, in the post-processing, it is conducted to verify the radioactivity level of the site before and after the work and decide to recycle or dispose the generated waste. For an accurate evaluation of gamma-ray emitting radionuclides, the measurement should be carried out near the region of interest on site, or a sample analysis should be performed in the laboratory. However, the region is inaccessible due to the safety-critical nature of nuclear facilities, and excessive radiation exposure to workers could be caused. In addition, in the case of subjects that may be contaminated inside such as pipe structures generated during decommissioning, surveying is usually done over the outside of them only, so the effectiveness of the result is limited. Thus, there is a need to develop a radiation measurement system that can be available in narrow space and can sense remotely with excellent performance. A liquid light guide (LLG), unlike typical optical fiber, is a light guide which has a liquid core. It has superior light transmissivity than any optical fiber and can be manufactured with a larger diameter. Additionally, it can deliver light with much greater intensity with very low attenuation along the length because there is no packing fraction and it has very high radiation resistant characteristics. Especially, thanks to the good transmissivity in UV-VIS wavelength, the LLG can well transmit the scintillation light signals from scintillators that have relatively short emission wavelengths, such as LaBr3:Ce and CeBr3. In this study, we developed a radiation sensor system based on a LLG for remote gamma-ray spectroscopy. We fabricated a radiation sensor with LaBr3:Ce scintillator and LLG, and acquired energy spectra of Cs-137 and Co-60 remotely. Furthermore, the results of gamma-ray spectroscopy using different lengths of LLG were compared with those obtained without LLG. Energy resolutions were estimated as 7.67%, 4.90%, and 4.81% at 662, 1,173, and 1,332 keV, respectively for 1 m long LLG, which shows similar values of a general NaI(Tl) scintillator. With 3 m long LLG, the energy resolutions were 7.92%, 5.48%, and 5.07% for 662, 1,173, and 1,332 keV gamma-rays, respectively.

Lately, Raman spectroscopy has become powerful tool for quality assessment of graphene analogues with identification of intensity ratio of Raman active D-band and G-band ( ID/IG ratio) as a vital parameter for quantification of defects. However, during chemical reduction of graphitic oxide (GrO) to reduced GrO (RGrO), the increased ID/ IG ratio is often wrongly recognized as defect augmentation, with “formation of more numerous yet smaller size sp2 domains” as its explanation. Herein, by giving due attention to normalized peak height, full-width half-maxima and integrated peak area of Raman D- and G-bands, and compliment the findings by XRD data, we have shown that in-plane size of sp2 domains actually increases upon chemical reduction. Particularly, contrary to increased ID/ IG ratio, the calculated decrease in integrated peak area ratio ( AD/AG ratio) in conjunction with narrowing of D-band and broadening of G-band, evinced the decrease in in-plane defects. Finally, as duly supported by reduction induced broadening of interlayer-spacing characteristic XRD peak and narrowing of ~ 43° centered XRD hump, we have also shown that the sp2 domains actually expands in size and the observed increase in ID/ IG ratio is indeed due to increase in across-plane defects, formed via along-the-layer slicing of graphitic domains.