In this work, a nanocomposite containing gold (Au) nanofibers decorated iron-metal–organic framework (Fe-MOF) was successfully synthesized for electrochemical detection of acetaminophen (AAP). The as-synthesized Au@Fe-MOF nanocomposite was confirmed by various characterization techniques. Morphological analysis showed that the Au nanofibers with an average size of less than 10 nm were dispersed on the Fe-MOF. Cyclic voltammetric analysis showed that the Au@Fe-MOF nanocomposite showed well-defined redox peaks with higher current than that of GCE and Fe-MOF. The Au@Fe-MOF/ GCE exhibited a linear range, sensitivity, and detection limit of 0.5–18 μM, 4.95 μM/μA/cm2, and 0.12 μM, respectively. The Au@Fe-MOF/GCE showed a very low response for the interference materials. The real sample analysis revealed that the Au@Fe-MOF/GCE showed good recovery towards the AAP in urine and paracetamol. Therefore, the developed sensor can be used for quality control of AAP.

Hydrogen-bonded organic frameworks (HOFs) are a new type of porous crystalline material that are constructed by intermolecular hydrogen bonding of organic building blocks to form twodimensional (2D) and three-dimensional (3D) crystalline networks. High-quality HOF single crystals are easily grown for direct superstructure analysis using single crystal X-ray diffraction, which is essential for revealing the relationship between structure and properties. The unique advantages of HOF, such as high crystallinity, porosity and fast regeneration, have allowed it to be used in a variety of applications including catalysis and gas separation. Squaric acid (SQA) is a non-carboxylic, organic acid with proton donor and acceptor ability which is known to take on a variety of coordination modes with metal ions. Pyrazine is a six-membered aromatic heterocycle bearing two nitrogen atoms, which has sp2 hybridized C atoms with C-H hydrogen bonds. This work describes the synthesis and structural characteristics of HOF based on squaric acid and pyrazine. Based on single crystal X-ray diffraction data, this MOF crystallizes in the triclinic P-1 space group. Each asymmetric unit is composed of H2SQ and pyrazine. All squaric acid molecules share one H atom with the N atom of pyrazine molecules. The layer distance between nearby O atoms from squaric acid in different layers equals 5.29 Å. Also, our HOF showed high adsorption capacity the during experiments. The composition and comparative characteristics of HOF are given using SCXRD, PXRD, SEM and UV-vis.

Lubricant oil waste contaminated with radioactive materials generated at nuclear facilities can be disposed of as industrial waste in accordance with self-disposal standards if only radioactive materials are removed. Lubricant oil used in nuclear facilities consists of oil of 75-85% and additives of 15-25%, and lubricant oil waste contains heavy metals, carbon, glycol, etc. In addition, lubricant oil waste from nuclear facilities contains metallic gamma-ray emission radionuclides including Co-60, Cs-137 and volatile beta-ray emission radionuclides such as C-14 and H-3, which are not present in lubricant oil waste from general industries and these radionuclides must be eliminated according to the Atomic Energy Act. In general industries, the wet treatment technologies such as acid-white soil treatment, ion purification, thin film distillation, high temperature pyrolysis, etc. are used as the refining technology of lubricant oil waste, but it is difficult to apply these technologies to nuclear industrial sites due to restrictions related with controlling the generation of secondary radioactive waste in sludge condition containing radionuclides of metal components, and limiting the concentration of volatile radioactive elements contained in refined oil to be below the legal threshold. In view of these characteristics, the refinement system capable of efficiently refining and treating lubricant oil waste contaminated with radioactive materials generated in nuclear facilities has been developed. The treatment process of this R&D system is as follows. First, the moisture in the radioactive lubricant oil waste pretreated through the preprocessing system is removed by the heated evaporating system, and the beta-emission radionuclides of H-3 and C-14 can be easily removed in this process. Second, the heated lubricant oil waste by the heated evaporating system is cooled through the heat exchanging system. Third, the particulate matters with gamma-ray emission radionuclides are removed through the electrostatic ionizing system. Forth, the lubricant oil waste is stored in the storage tank and the purified lubricant oil waste is discharged to the outside after sampling and checking from the upper, middle and lower positions of the lubricant oil waste stored in the storage tank. Using this R&D system, it is expected that the amount of radioactive waste can be reduced by efficiently refining and treating lubricant oil waste in the form of organic compounds contaminated with radioactive materials generated in nuclear facilities.

Organic complexing agents may affect the mobility of radionuclides at low- and intermediate-level radioactive waste repositories. Especially, isosaccharinic acid (ISA) is the main cellulose degradation product under high pH conditions in cement pore water. ISA can combine with radionuclides and form stable complexes that adversely influence adsorption in the concrete phase, resulting in radionuclides to leach to the near- and far-fields of repositories. This study focuses on investigating the sorption of ISA onto engineered barriers such as concrete, thereby studying adsorption isotherms of ISA on concrete and comparing various isotherm models with the experimental data. The adsorption experiment was conducted in three background solutions, groundwater (adjusted to pH 13 using NaOH), State 1 (artificial cement pore water, pH 13.3), and State 2 (artificial cement pore water, pH 12.5), in a batch system at a temperature of 20°C. Concrete was characterized using BET, Zeta-potential analyzer, XRD, XRF, and SEM-EDS. ISA concentrations were detected using HPLC. The experimental data were best fitted to one-site Langmuir isotherm; On the other hand, either two-site isotherm or Freundlich isotherm couldn’t give reasonable fitting to the experimental data. The observed ISA sorption behavior on concrete is crucial for the disposal of radioactive waste because it can significantly lower the concentration of ISA in the pore water. Although one-site Langmuir isotherm might effectively represent the sorption behavior of ISA on concrete, the underlying mechanism is still unknown, and further investigation should be done in the near future.

Engineered barriers (concrete and grout) in Low- and Intermediate-Level Waste (L/ILW) disposal facilities tend to degrade by groundwater or rainfall water over a long period of time. During the degradation process, radionuclides stored in the disposal facility might be released into the pore water, which can pass through the natural rock barriers (granite and sedimentary rock) and may reach the near-field and far-field. In this transportation, radionuclide might be sorbed onto the engineered and natural rock barriers. In addition, the organic complexing agent such as ethylenediaminetetraacetic acid (EDTA) and α-isosaccharinic acid (ISA), is also present in pore water, which may affect the sorption and mobility of radionuclide. In this study, the sorption and mobility of 90Sr under different conditions such as two pHs (7 and 13), different initial concentrations of organic complexing agents (from 10-5 M to 10-2 M), and solutions (groundwater, pore water, and rainfall water) were investigated in a batch system. The groundwater was collected at the L/ILW disposal facility located at Gyeongju in South Korea. The pore water and rainfall water were artificially made in the laboratory. The concrete, grout, granite, and sedimentary rock samples were collected from the same study sites from where the groundwater was collected. The rock samples were crushed to 53-150 micrometers and were characterized by XRD, XRF, SEM-EDS, BET, and zeta potential analyzer. 90Sr concentration was determined using liquid scintillation counting. The sorption of 90Sr was described by distribution coefficients (Kd) and sorption reduction factor (SRF). In the case of EDTA, the Kd values of 90Sr remained constant from 10-5 M to 10-3 M and tended to decrease at 10-2 M, while in case of ISA the Kd values decreased steadily as the concentration of ISA was increased from 10-5 M to 10-3 M; However, a sudden reduction in the Kd values were observed above 10-2 M. In comparison to EDTA, ISA gave a higher SRF of 90Sr. Therefore, from the above results, it can be concluded that the presence of ISA has a greater effect on the sorption and mobility of radionuclide in the solutions than EDTA, and the radionuclide may reach near- and far-field of the L/ILW disposal facility.

Radionuclides can be leached into groundwater or soil over a long period of time due to unexpected situations even after being permanently disposed of in a repository. Therefore, it is necessary to investigate the mobility of radionuclides for the safety assessment of radioactive waste disposal. In this study, the effects of organic complexing agents such as ethylenediaminetetraacetic acid (EDTA) and isosaccharinic acid (ISA) on the sorption behavior of 239Pu and 99Tc over cementitious (concrete and grout) and natural rock samples (granite and sedimentary rock) were investigated in batch sorption experiments. For characterization of rock samples, XRD, XRF, FT-IR, FE-SEM, BET, and Zeta-potential analyses were performed. For the evaluation of mobility, the distribution coefficient (Kd) was selected and compared. The adsorption experiment was carried out at two pHs (7 and 13), a temperature of 20°C, and a range of organic complexing agents concentrations (10-7~10-2 M and 10- 5~10-2 M for 239Pu and 99Tc, respectively). The radionuclides concentrations in adsorption samples were analyzed using ICP-MS. The Kd values for 239Pu in all rock samples reduced significantly due to the presence of EDTA, even at low concentrations such as 10-5 M. In the case of ISA, the limiting noeffect concentration was much higher than that of EDTA. On the other hand, 99Tc showed relatively lower Kd values than 239Pu, and the sorption behavior of 99Tc was almost unaffected by the organic complexing agents for all rock samples. Therefore, it is possible to assume that the increased mobility of radionuclides, especially, 239Pu, in groundwater caused by the lowering of sorption at even low concentrations of organic complexing agents may result in the transport of radionuclides to the nearand far-field location of the repository.

Organic complexing agents which are contained in the radioactive waste can form the complex with radionuclides and enhance the solubility of radionuclides. The mobility of radionuclides to the far-field from the repository will be increased by radionuclide-ligand complex formation. Therefore, the assessment of the radionuclides’ solubility should be performed in the presence of organic complexing agents. In this study, five radionuclides (cobalt, strontium, iodine, cesium, and uranium) and three organic complexing agents (ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA)) were selected as model radionuclides and organic complexing agents, respectively. For simulating the in-situ condition, the groundwater near the repository was collected and applied in solubility experiments and the solubility was measured in various environmental conditions such as different pHs (7, 9, 11, and 13), temperatures (10°C, 20°C, and 40°C), and a range of organic complexing agent concentrations (10-5, 10-4, 10-3, and 10-2 M). In cases of cesium and iodine, they were very soluble in all conditions, and the effect on their solubilities was not observed. However, at high pHs, cobalt and strontium showed lower solubilities than at neutral pH and the solubility enhancement by the organic complexing agents was significant. Moreover, the effects of each organic ligand showed obvious differences and were in the order of EDTA > NTA > ISA. The solubility of uranium was increased with increasing the organic ligand concentration at lower pHs, but the organic complexing agents did not cause a remarkable difference at high pHs. According to these results, the presence of complexing agents could enhance the radionuclides’ solubility and increase the potential to release the radionuclides to the far-field from the repository. Solubility experiments of other major radionuclides in the repository are in progress.

Time-resolved laser fluorescence spectroscopy (TRLFS) and excitation-emission matrix (EEM) spectroscopy were used to study the interaction of U(VI) and natural organic matters (NOMs) in groundwater. Various types of groundwaters (DB-1, DB-3 from KURT site and OB-1, OB-3 from a U deposit in Ogcheon metamorphic belt) were used as samples. Pulsed Nd-YAG laser at 266 nm (Continuum Minilite) was used as the light source of TRLFS. The laser pulse energy of 1.0 mJ was fixed for all measurements. The luminescence spectrum was recorded using a gated intensified chargecoupled device (Andor, DH-720/18U03 iStar 720D) attached to the spectrograph (Andor, SR-303i). EEM spectra were measured using a spectrofluorometer (Horiba Scientific, Aqualog) equipped with a 150 W ozone-free xenon arc lamp. Excitation spectra were recorded by scanning the excitation wavelength from 200 to 500 nm. Emission spectra were measured using a CCD in the wavelength range of 242–823 nm. In the case of the recently collected DB-1 samples, it was observed that the U and NOM quantities decreased compared to the samples collected before 2016. For some DB-1 samples, the amount of dissolved organic carbon indicating the presence of NOM was significantly reduced, and changes consistent with this phenomenon were observed in the EEM spectrum. The time-resolved luminescence characteristics (peak wavelengths and lifetime) of U(VI) in the DB-1 samples agree well with those of Ca2UO2(CO3)3(aq). This U(VI) species remains stable, even in samples taken five years ago. The estimated amounts of U and NOM from the spectroscopic data of DB-3, OB-1, and OB-3 samples are relatively low compared to DB-1 samples. When a known amount of U(VI) was mixed in each groundwater, the time-resolved luminescence spectrum exhibited a characteristic spectral shape different from the expected luminescence intensity. This phenomenon is presumed to be due to the interaction between U(VI) and NOM in groundwater. The results of this study suggest that the chemical speciation of NOM as well as U(VI) is required to understand U behavior in groundwater.

최근 비풀러렌 전자수용체 소재 개발로 태양전지 및 광검출기 등 유기광다이오드 분야의 상당한 진보를 나타내고 있 다. 비풀러렌 소재의 자유로운 구조 개질 가능성을 바탕으로 흡광대역 자유 제어가 가능한 장점으로, 기존 태양전지 에서 구현이 힘들었던 고성능 반투명 태양전지, 실내 저조도 태양전지, 파장선택적 광검출기 등 다양한 응용을 가능 하게 한다. 본 리뷰에서는 유기태양전지를 비롯한 유기광다이오드의 광활성층에 활용되는 유기반도체 소재의 최신 연 구동향에 대해 다루고자 한다.

본 연구는 극지 식물플랑크톤의 자외선 영향을 파악하기 위해, Phaeocystis antarctica와 Phaeocystis pouchetii를 대상으로 유색 용존 유기물의 생산과 광반응성을 평가하였다. 강한 자외선에 노출 배양 시, 가시광선 파장대에서 유색 용존 유기물의 흡광도는 두 식물플랑크 톤 모두 배양 초기에 비해 48시간 동안 감소하였다. 반면, 자외선 파장에서는 P. antarctica는 48시간 배양 후, 유색 용존 유기물의 흡광도는 초기 농도에 비해 약 30% 감소하였지만, P. pouchetii의 흡광도는 오히려 10% 증가한 경향을 보였다. 이 결과들은 강한 자외선에 노출될 경 우, P. antarctica이 생산한 유색 용존 유기물은 광분해에 의한 감소로 인해 해수 중 수중 생태계에 자외선 차단 효과는 감소하는 반면, P. pouchetii가 생산한 유색 용존 유기물에 의한 광보호 효과가 더 효율적임을 알 수 있었다. 또한, 자외선 영향 하에서 배양된 P. pouchetii의 배 양액에서 시간에 따라 증가한 유색 용존 유기물의 형광 특성이 지구 거대물질로 알려진 humic-like (C-peak)와 일치하여, 이는 자외선 차단 물질로 알려진 MAAs 생물 생산에 의한 것임을 확인하였다. 이는 기후변화에 의한 성층화가 강화되는 극지 해양환경에서, 광반응성이 낮은 P. pouchetti가 용존 유기물의 증가에 기여할 수 있을 것으로 기대된다.

The team has studied the relationship between the ability of the coals to be dissolved in crude anthracene oil and their composition. The coal samples taken from different deposits in Russia and Mongolia were characterized by different stages of metamorphism and tested by the Fourier transform infrared spectroscopy and Carbon-13 nuclear magnetic resonance. The data of a correlation analysis enabled us to find out that an amount of aromatic structures in coal macromolecules provided the main influence on the thermal dissolution of the coals. The middle-rank coals had the highest rates of coal organic matter transfer to liquid products. The data showed that the dissolution process was accompanied by destruction of weak bonds among aliphatic groups. The amount of methylene groups in the aliphatic part of coal macromolecules had a direct impact on conversion of the coal organic matter into soluble products.