Chelating agents, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and nitrilotriacetic acid (NTA) are widely used in industry and agriculture as water softeners, detergents, and metal chelating agents. In wastewater treatment plants, a significant amount of chelating agents can be discharged into natural waters because they are difficult to degrade. Since those compounds affect the mobility of radionuclides or heavy metals in decontamination operations at nuclear facilities and radioactive waste disposal, quantification of the amount of ligand is very important for safe nuclear waste management. To predict the behavior of the main complexation in sample matrices of radioactive wastes, it is essential to evaluate the distribution of the metal-chelating species and their stabilities in order to develop analytical techniques for quantifying chelating agents. We have investigated to collect information on the pH speciation of metal chelation and the stability constants of metal complexes depending on three chelating agents (EDTA, DTPA, and NTA). For example, Zhang’s group recently reported that the initial coordination pH of Cu(II) and EDTA4− is delayed with the addition of Fe(III), and the pH range for the stable existence of [Cu(EDTA)]2− is narrowed compared to when it is alone in the sample matrix. The addition of Fe(III) clearly impacts the chemical states of the Cu(II)-EDTA solution. Additionally, Eivazihollagh’s group demonstrated differences in the speciation and stability of Cu(II) species between Cu(II) and three chelating ligands (EDTA, DTPA, and NTA). This study will be greatly helpful in identifying the sample matrix for binding major chelating agents and metals as well as developing chemically sample pretreatment and separation methods based on the sample matrix. Finally, these advancements will enable reliable quantitative analysis of chelating agents in decommissioning radioactive wastes.

During the operation of a nuclear power plant (NPP), corrosion products called CRUD (Chalk River unidentified deposit) accumulate on the surface of the primary system. The CRUD components of pressurized light water reactors or heavy water reactors, represented by (NixFe1-x)(FeyCr1-y)2O4, are composed of Fe3O4, NiFe2O4, FeCr2O4, NiCr2O4, etc. Radionuclide such as Co-60 are deposited within this CRUD, so the entire deposited material must be dissolved and removed for decontamination. Chemical decontamination has the advantage of being able to decontaminate a wide metal surface, but has the disadvantage of generating a large amount of secondary waste. Recently, chemical decontamination methods that add an electrodynamic process are being studied to overcome these shortcomings. This technology is a method of dissolving CRUD by applying an electric field in the anodic compartment of a cell separated by CEM. It is a method of accelerating CRUD dissolution by generating a large amount of hydrogen ions in the anodic compartment. Dissolved metal ions pass through the CEM (cation exchange membrane) and move to the cathodic compartment (pH > 12), where they are removed by adsorption or precipitation process. Therefore, the speciation characteristics between decontamination agent (oxalic acid) and metal ions are very important. In this study, we investigated the speciation characteristics of Fe(II), Ni(II), Co(II) - oxalate, which are important complex species in CRUD dissolution cells. The thermodynamic equilibrium constant for hydrolysis of each ion and of M(II)-oxalate were collected and speciation characteristics were analyzed using the MINEQL 5.0 program. From the speciation characteristics of M(II)-oxalate, effective radionuclide removal methods in an electrodynamic cell were considered.

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.

Two Grapholita congeners, G. dimorpha and G. molesta, are internal fruit feeders and their young larvae cause serious damages to pome and stone fruits in Korea. They share similar morphological and biological characters not to be easily discriminated. We needed to develop molecular markers using diagnostic primers and PCR-RFLP with specific sequences in ND4 region. Two species have similar sex pheromone components (Z8-12:Ac and E8-12:Ac) although their composition ratios are different. In fields, G. molesta males were more captured in lures with higher Z8 component ratio than G. dimorpha males. Addition of Z8-12OH, minor sex pheromone component prevented G. dimorpha from capturing G. molesta males. In electroantennogram (EAG) bioassay, these two species males showed significant electric responses in their own sex pheromone ratios. An addition of Z8-12:OH to the major sex pheromone components significantly suppressed the EAG response of G. dimorpha, while it did not change that of G. molesta. A deep sequencing analysis of transcripts of both species pheromone glands identified sex pheromone biosynthesis genes including fatty acid synthase, desaturases, fatty acyl reductase (FAR), and aldehyde reductase. The presence of delta 10 desaturase in both species suggests that a double bond at C8 position in dodecenyl acetate is produced by desaturation at C10 position of tetradecenyl fatty acid and subsequent β-oxidation, which is then reduced at carboxylic acid by FAR to be acetylated by acetyl transferase. High sequence variation of FAR genes of G. molesta and G. dimorpha suggests their stereoisomer substrate preference, which may exert a driving force for this speciation with delta 10 desaturase.

To understand the evolution and speciation of closely related species, a multiple approach encompassing morphological, behavioral, and genetic analyses is necessary. In Korea, three species of Loxoblemmus crickets occur widely. L. campestris and L. equestris are morphologically indistinguishable, whereas males of L. doenitzi are different from the other two species in head morphology. The genetic analyses using the partial mitochondrial COI sequences showed that L. doenitzi diverged off earlier than L. campestris and L. equestris. The analyses of laboratory recordings revealed that distributions of calling song characters generally overlapped among three cricket species. However, the number of pulses in a chirp was two in L. doenitzi and four in L. campestris, but it was greater than or equal to six in L. equestris. Provided that females make mate choice based on this calling song character, the differentiation in this character may lead to premating reproductive isolation and may have evolved during the speciation proccess in these closely related species.

Cryptic species are hardly distinguished by their morphology but reproductively isolated. To understand the evolution and speciation of cryptic species, differentiations between cryptic species should be studied using multiple approaches including morphological analysis. Two of three species under the genus Loxoblemmus in Korea are morphologically similar and may constitute the cryptic species. We studied the differentiations in morphology, calling songs, and genetic sequences to understand patterns of speciation in these three species. Although L.doenitzi was easily distinguished from the other two species based on morphology, the distributions of the number of file teeth and wing morphology overlapped in L. campestris and L. equestris. However, there were clear differentiations in some calling song characters among three cricket species. The number of pulses in a chirp was two in L.doenitzi and four in L. campestris, but that was greater than or equal to six in L. equestris. The genetic sequence analyses using 16S rRNA and COI barcode revealed that L. doenitzi diverged off earlier from the other two species. Calling songs of L. campestris and L. equestris largely differed in spite of their short divergence time. Our results suggest that the speciation processes may involve differentiation in calling songs in the Loxoblemmus complex.

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.

제주도 척추동물상에 관한 문헌을 정리한 결과 제주도산 담수어류는 9목 12과 24종, 양서류는 2목 6과 9종, 파충류는 2아목 5과 10종, 조류는 18목 49과 4아과 236종, 포유류는 6목 9과 16종으로 총 35목 2아목 80과 4아과 295종이 분포, 서식하고 있음이 확인되었다. 제즈도의 특산 척추동물은 제주족제비(Mustela sibirica quelpartis), 제주등줄쥐(Apodemus agrarius chejuensis), 제주멧밭쥐(Micromys minutus hertigi) 및 제주땃쥐(Crocidura russula quelpartis)등 4종의 포유류가 있고, 조류는 제주오목눈이(Ageithalos caudatus trivirgatus), 제주동고비(Sitta europaea bedfordi), 제주밀화부리(Eophona personata personfumigatus), 제주박새(Parus major minor) 및 제주휘파람새(Cettia diphone antans) 등 7종이며, 양서류는 유미류의 제주도롱뇽(Hynobius leechii quelpartis) 1종 등, 총 12아종이 서식하고 있으며, 한편 본토에는 서식하지 않고 제주도에만 서식하는 종은 비바리뱀(Sibynophis collaris)과 무태장어(Anguilla mauritiana)이다. 제주도는 신생대 3기말에서부터 4기에 걸쳐 형성되었으며, 지질학적으로 빙하기가 시작되는 Donau 빙하기 이후부터 척추동물이 이주하여서식하기 시작하였고, 제주도가 형성된 후 척추동물이 생존하기에 적합ㅎ한 환경이 조성되면서 중기 홍적세 이후 현세로부터 약 30만년전부터 빙하기와 간빙기의 반복과 더불어 본토집단과 지리적 격리가 거듭되면서 척추동물의 종분화가 진행되고 있다.

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.

The re-emission of mercury (Hg), as a consequence of the formation and dissociation of the unstable complex HgSO3, is a problem encountered in flue gas desulphurization (FGD) treatment in coal-fired power plants. A model following a pseudo-second-order rate law for Hg2+ reduction was derived as a function of [SO32-], [H+] and temperature and fitted with experimentally obtained data to generate kinetic rate values of (0.120 ± 0.04, 0.847 ± 0.07, 1.35 ± 0.4) mM-1 for 40°, 60°, and 75℃, respectively. The reduction of Hg2+ increases with a temperature increase but shows an inverse relationship with proton concentration. Plotting the model-fitted kinetic rate constants yields ΔH = 61.7 ± 1.82 kJ mol-1, which is in good agreement with literature values for the formation of Hg0 by SO32-. The model could be used to better understand the overall Hg2+ re-emission by SO32- happening in aquatic systems such as FGD wastewaters.

Extensive land subsidence and submergence occurred in the coal mining areas (Huainan and Huaibei) in Anhui Province, China. As a result, lots of subsided lakes have been formed due to their unique geological features. Four typical lakes were selected to evaluate the internal phosphorus (P) releasing risk based on the specification of P, Fe and Al from the sediments. Sediment P, Fe and Al in the top 5 cm were extracted sequentially, aiming at obtained fractionation for environmental indicators. Experiments of P isothermal adsorption were conducted to characterize P sorption ability. The results suggested that P internal loading potential was related to Al and Fe compounds in sedimentary environments of soil inundation, primarily determined by regional soil properties. Internal P releasing risk was mainly controlled by the properties of calcareous soils in the Huaibei; whereas controlled by Fe and Al in the Huainan. Overall, the obtained results fit well with the model proposed by Kopáček et al.(2005), which predicted low P flux as molar ratio of [NH4Cl-Al + BD-Al + NaOH-Al] : [NH4Cl-Fe + BD-Fe] >3 or [NaOH-Al] : [NH4Cl-P + BD-P] >25 from sediments when anoxia is developed. However, this threshold has site-specific flexibility, with its lower limit approaching 20:1 applicable for the three lakes in Huainan. Higher loads of external input organic matters or enriched Fe oxides bound P tend to change this limit and lead to internal loading risk with environmental anoxia.

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.

이 논문은 온산공업단지 내 화강암의 풍화 및 토양화 과정, 그리고 토양 내 중금속 오염과 토양 광물간의 관계에 관한 연구이다. 프로화일 연구를 위해 각 깊이별로 토양시료를 채취하여 각 샘플에 대한 실험분석을 실시하였다. X선 회절분석 결과 주 구성 점토광물은 캐올린 광물과 버미큘라이트, 그리고 미량의 일라이트이다. 포름아마이드 처리를 통해 프로화일 내 토양 중의 캐올린 광물의 종류에 대해 분석한 결과 프로화일 하부에 존재하는 캐올린 광물은 대부분 할로이사이트 임이 밝혀졌으며, 지표면으로 갈수록 상대적으로 캐올리나이트에 대한 할로이사이트의 양이 감소하는 경향을 보이는데, 이는 상부로 갈수록 할로이사이트에서 캐올리나이트로의 전환이 이루어지고 있음을 의미한다. 110℃, 300℃, 550℃ 열처리를 한 결과 X선회절분석 그래프 상의 10 a에서 14 a 사이의 피크가 분화된 형태를 보여주는 것이 관찰된다. 이는 시료상에 수산화알루미늄 혼합층 버미큘라이트가 존재함을 지시한다. 이것은 구연산나트륨 처리실험을 통해 버미큘라이트 층간 불순 알루미늄 이온을 추출하여 원형상으로 전환시킴으로써 열처리시 14 a피크가 다시 10 a으로 변화하는 것을 관찰함으로써 재확인하였다. 토양의 수소이온농도 분포 양상이 하부에서 3.9, 상부에서 3.6으로 상부로 갈수록 산성화경향이 심해지는 경향을 보여주는데, 이는 산성화된 토양에서 안정적으로 나타나는 수산화알루미늄 혼합층 버미큘라이트의 존재를 뒷받침하고 있다. 토양 내 중금속 이온의 존재양상에 대한 연구를 위해 연속추출실험을 실시하였다. 그 결과 상대적으로 많은 양의 중금속 이온이 프로화일의 상부의 철/망간 산화물과 유기물에 흡착되어 있으며 점토광물에는 적은 양만이 흡착되어 있는 것으로 밝혀졌다. 이러한 결과는 대부분의 중금속 오염물들이 상부 토양에 농집되어 있고 점토광물에는 낮은 중금속 함량을 보여주는 것은 산성화된 토양을 이루고 있는 주 점토광물인 캐올린광물과 수산화알루미늄 혼합층 버미큘라이트가 낮은 흡착능력을 가지고 있기 때문인 것으로 판단한다.

The Janghang smelter is the first lead, zinc and copper smelting facility in Korea which was operated for a half century from 1936 to 1989. The clay minerals and their heavy metal association in the soil profile around the smelter have been studied using XRD, EPMA, SEM-EDS, TEM, EPR and sequential extraction techniques. The soils in A horizon are highly acidic showing pH 4.45. The pH is going up with increasing depth. They have residual water contents of 1.18-1.51 wt%, loss on ignition of 6.32-7.79 wt%, and carbon contents of 0.08-0.88 wt%. Soils consist of quartz, feldspar, muscovite, kaolinite, vermiculite, biotite, chlorite, goethite and hematite in the decreasing abundance. The contents of clay minerals, especially vermiculite and chlorite, decrease with increasing depth. Sequential extraction experiments for the profile samples show that heavy metals (Zn, Cu, Pb, Cd) are highly concentrated in the A horizon of the soil profile as water-extractable (mostly amorphous), MgCl2-extractable (exchangeable in clay minerals), and organic phases. The heavy metal contents decrease with increasing depth. It suggests that the heavy metals are mainly associate with clay minerlas in an exchangeable state. It is also noted that heavy metals are highly concentrated in the manganese and iron oxide phases.