For the safety assessment of the high-level radioactive waste (HLRW) disposal, the thermodynamic data such as solubility products, formation constants of complexes, redox equilibrium constants of radionuclides, and their reaction enthalpy and entropy are required. In order to recommend and summarize the reliable data, thermodynamic databases (TDB) have been persistently developed through the OECD-NEA TDB projects and an updated TDB of actinides has been recently published in 2020. To date, reliable data for Pu reactions are scarce due to the possibility of coexistence of four different oxidation states, Pu(III-VI) by redox equilibria in solutions. To determine the thermodynamic data for the reaction of each Pu oxidation state, it is necessary to precisely control the oxidation state and quantitatively analyze all reactants, products and bi-products by using highly sensitive speciation techniques. Since 2004, the nuclear chemistry research team in KAERI has been focused on developing techniques for the sensitive chemical speciation by using laser-based spectroscopy and determining thermodynamic data of actinides such as U, Pu, Am. In this paper, chemical speciation and thermodynamic studies on Pu in KAERI are reviewed. A combination of a commercial spectrophotometer and a capillary cell was adopted for a sensitive chemical speciation of Pu(III-VI) in solutions. A sensitive detection of trace amount of Pu colloids was carried out with the laser-induced breakdown detection (LIBD) system. Pu(VI) complexation with hydroxide or carbonate ions were investigated under strong oxidation conditions controlled with hypochlorite (NaOCl). The solubility product of Pu(OH)3(am) and formation constant of Pu(III)-OH speices were determined by a combination of wet-chemistry experiments and several analysis methods of spectrophotometry, LIBD, radiometry under a strong reducing condition controlled by electrochemistry. More recently, we reported the reaction enthalpy and entropy data for the formation of Pu(OH)2+ and the dissolution of Pu(OH)3(am). A preliminary data for reaction between Pu(III) and organic matter will be presented.

본 연구의 목적은 휘발성 유기화합물(VOC)과 먼지(PM)의 배출원 프로파일로부터 화학종 분류를 할당하고, 성김 행렬 조작자 핵심 배출량 시스템(SMOKE) 내에 배출원 분류코드에 따른 배출원 프로파일의 화학종 분류와 시간분배계수를 수정하는 것이다. 기솔린, 디젤 증기, 도장, 세탁, LPG 등과 같은 VOC 배출원 프로파일로부터 화학 종 분류는 탄소 결합 IV (CBIV) 화학 메커니즘과 주 규모 대기오염연구센터 99 (SAPRC99) 화학 메커니즘을 위해 각각 12종과 34종을 포함한다. 또한 토양, 도로먼지, 가솔린, 디젤차, 산업기원, 도시 소각장, 탄 연소 발전소, 생체 연소, 해안 등과 같은 PM2.5 배출원 프로파일로부터 화학종 분류는 미세 먼지, 유기탄소, 원소 탄소, 질산염과 황산염의 5종으로 할당하였다. 게다가 점 및 선 배출원의 시간 프로파일은 2007년 수도권 지역에서의 굴뚝 원격감시시스템(TMS)과 시간별 교통 흐름 자료로부터 구하였다. 특별히 점 배출원에 있어 오존 모델링을 위한 시간분배계수는 굴뚝 원격감시시스템 자료의 NOX 배출량 인벤토리에 근거하여 추정하였다.

시간분해 레이저 유도 형광 분광학을 이용하여 UO22+, UO2(OH)+, (UO2)2(OH)22+, (UO2)3(OH)5+와 같은 우라늄(VI) 화학종 규명 연구를 수행하였다. 들뜸 파장의 변화에 따른 화학종 규명 감도를 조사하였다. 266 nm의 들뜸 파장을 이용할 경우, 나노 몰 농도의 U(VI) 화합물을 구분할 수 있는 화학종 규명 감도를 얻었다. 이온 세기가 0.1 M, pH가 1인 조건에서 UO22+ 이온의 형광 스펙트럼과 형광 수명을 측정하였다. 488, 509, 533, 559 nm 파장의 특징적인 형광 봉우리를 관측하였고, 측정한 형광 수명은 1.92±0.17 ㎲ 이었다. U(VI) 가수분해 화합물의 형광 스펙트럼과 형광 수명의 변화를 이 값을 기준으로 비교하였다. 장파장 방향으로 이동한 형광 봉우리와 길어진 형광 수명을 가진 가수분해 화합물의 특징적인 양상을 보고한다.

For 26 soil series distributed more than 1% among 63 soil series in Jeju Island, natural uncultivated soil samples were collected. For these soils, the chemical speciation of eight heavy metals (Cd, Cr, Cu, Mn, Ni, Pb, V, and Zn) was examined. Further, the Plant Bioavailability (PB) and Mobility Factor (MF) of these heavy metals were evaluated using Tessier’s 5-step sequential extraction method (exchangeable, carbonate, reducible (bound to Fe/Mn oxides), oxidizable (bound to organic matter), and residual fraction). The main form present was residual fraction for Cd and Zn; residual and oxidizable fractions for Cr, Cu, Ni, and Pb; reducible fraction for Mn; and carbonate fraction for V. The average plant availability and average mobility factor were found to be V (57.37%) > Zn (12.49%) > Cd (11.76%) > Cu (11.19%) > Pb (9.37%) > Cr (9.09%) > Mn (3.13%) > Ni (2.63%), and Mn (61.04%) > V (59.94%) > Zn (31.54%) > Cd (17.65%) > Cr (15.66%) > Ni (13.89%) > Pb (13.80%) > Cu (13.53%), respectively.

Airborne particles collected from a heavily industrialized site were analyzed by chemical speciation of seven trace metals: Pb, Cd, Cr, Cu, Ni, Zn, and As. The average concentrations were as follows: Zn, 502.0 ± 230.7; Pb, 176.5 ± 310.9; Cu, 111.9 ± 82.7; As, 38.0 ± 31.0; Cr, 21.5 ± 24.4; Cd, 20.8 ± 17.4; and Ni, 11.4 ± 8.4 ng/m3. The median enrichment factor (EF) values of Cd (7,280), As (1,030), Cu (215), Zn (214), and Pb (143), with respect to iron, were much larger than 100. We observed that Cd was found in the soluble and exchangeable form (56.9%), and that Pb and Cr were found in carbonates, oxides and the reducible form (69.8% and 61.1%, respectively). These two forms, which are the most easily absorbed into human body tissue, predominated in most of the trace metals investigated in this study.

In order to predict the distribution of chemical species of copper and cadmium in water, conditional stability constant and complexation capacity between copper or cadmium and natural aquatic sediment have been determined in a shallow lake in Haman, Kyungnam. Kinetic parameters were calculated by Langmuir isotherm equation. Conditional stability constant was log K_cdses=4.78 and log K_cdsed=4.45. Complexation capacity was 1.70×10 exp (-4) moles/g for copper and 5.54×10 exp (-4) moles/g for cadmium. Accuracy of experimental values of conditional stability constant was checked by comparing the calculated concentration of the metals with the measured one. Relatively good agreement between these values was obtained. Relative errors were 8.9% for copper and 6.5% for cadmium. Data of the measured conditional stability constant were put into data base of MINEQL computer program, and concentration of various chemical species of copper and cadmium in a model aquatic system was calculated. Aquatic sediment was associated with copper at the concentration of 10^-5M(0.059g/ℓ) and with cadmium at the concentration of 10^-6M(0.018g/ℓ), and it significantly influenced on the distribution of chemical species of the metals. This result showed that prediction of chemical species of the heavy metals in an aquatic system should be taken into account the influence of the sediment.