• Title/Summary/Keyword: Complexation

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Radioanalytical and Spectroscopic Characterizations of Hydroxo- and Oxalato-Am(III) Complexes (방사분석과 분광학을 이용한 Am(III) 가수분해와 옥살레이트 착물 화학종 연구)

  • Kim, Hee-Kyung;Cho, Hye-Ryun;Jung, Euo Chang;Cha, Wansik
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.16 no.4
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    • pp.397-410
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    • 2018
  • When considering the long-term safety assessment of spent-nuclear fuel management, americium is one of the most radio-toxic actinides. Although spectroscopic methods are widely used for the study of actinide chemistry, application of those methods to americium chemistry has been limited. Herein, we purified $^{241}Am$ to obtain a highly pure stock solution required for spectroscopic studies. Quantitative and qualitative analyses of purified $^{241}Am$ were carried out using liquid scintillation counting, and gamma and alpha radiation spectrometry. Highly sensitive absorption spectrometry coupled with a liquid waveguide capillary cell and time-resolved laser fluorescence spectroscopy were employed for the study of Am(III) hydrolysis and oxalate (Ox) complexation. $Am^{3+}$ ions under acidic conditions exhibit maximum absorbance at 503 nm, with a molar absorption coefficient of $424{\pm}8cm^{-1}{\cdot}M^{-1}$. $Am(OH)_3(s)$ colloidal particles formed under near neutral pH conditions were identified by monitoring the absorbance at around 506-507 nm. The formation of ${Am(Ox)_3}^{3-}$ was detected by red-shifts of the absorption and luminescence spectra of 4 and 5 nm, respectively. In addition, considerable enhancements of the luminescence intensities were observed. The luminescence lifetime of ${Am(Ox)_3}^{3-}$ increased from 23 to 56 ns, which indicates that approximately six water molecules are replaced by carboxylate ligands in the inner-sphere of the Am(III). These results suggest that ${Am(Ox)_3}^{3-}$ is formed through the bidentate coordination of the oxalate ligands.

Effects of free metal ions and organo-metal complexes on the absorption of lead and cadmium by plants (식물에 의한 납, 카드뮴 흡수 기작에 미치는 자유이온 및 유기산-중금속 복합체의 영향)

  • Lee, Mina;Seo, Byounghwan;Kim, Kwon-Rae
    • Journal of Applied Biological Chemistry
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    • v.64 no.2
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    • pp.159-164
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    • 2021
  • Heavy metals exist in soils in various chemical forms including free metal ions and organo-metal complexes. The ratio of free metal ions has been known to be highly associated with the plant absorption of heavy metals. This study aims to understand the effect of free ions and organo-metal complexes on the absorption of lead (Pb) and cadmium (Cd) by plants. For this, lettuce grown in a hydroponic system for 28 days was consequently grown another 48 hours using Pb and Cd solutions. The ratios of free ion to organo-metal complexes in the solutions were adjusted at 100:0, 90:10, 70:30, 60:40 by four different organic acids (citric, oxalic, acetic, and humic acid). After that, the concentration of Pb and Cd in lettuce were analyzed. The Pb and Cd absorption by lettuce was more relied on the types of organic acids treated and the type of metals rather than the ratio of free metal ions. For example, citric acid increased the Pb absorption while it decreased the Cd absorption by lettuce. There was no significant relationship between free metal ion ratios and both Pb and Cd uptake by lettuce. It could be explained that citric acid, a relatively higher molecular weight organic acid, has higher ion binding capacity, so it forms organo-Pb complex easily due to the higher affinity of Pb on the binding site in comparison with Cd. Consequently, this complexation would assist Pb uptake by lettuce.

Application of Nano Fe°-impregnated Biochar for the Stabilization of As-contaminated Soil (비소 오염토양의 안정화를 위한 나노 Fe° 담지 바이오차 적용 연구)

  • Choi, Yu-Lim;Angaru, Ganesh Kumar Reddy;Ahn, Hye-Young;Park, Kwang-Jin;Joo, Wan-Ho;Yang, Jae-Kyu;Chang, Yoon-Young
    • Journal of Environmental Impact Assessment
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    • v.29 no.5
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    • pp.350-362
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    • 2020
  • In this study, nano Fe°-impregnated biochar (INPBC) was prepared using pruning residues and one-pot synthetic method and evaluated its performance as an amendment agent for the stabilization of arsenic-contaminated soil. For the preparation of INPBC, the mixture of pruning residue and Fe (III) solution was heated to 220℃ for 3hr in a teflon-sealed autoclave followed by calcination at 600℃ under N2 atmosphere for 1hr. As-prepared INPBC was characterized using FT-IR, XRD, BET, SEM. For the stabilization test of as-prepared INPBC, As-contaminated soils (Soil-E and Soil-S) sampled from agricultural sites located respectively near E-abandoned mine and S-abandoned mine in South Korea were mixed with different of dosage of INPBC and cultivated for 4 weeks. After treatment, TCLP and SPLP tests were conducted to determine the stabilization efficiency of As in soil and showed that the stabilization efficiency was increased with increasing the INPBC dosage and the concentration of As in SPLP extractant of Soil-E was lower than the drinking water standard level of Ministry of Environment of South Korea. The sequential fractionation of As in the stabilized soils indicated that the fractions of As in the 1st and 2nd stages that correspond liable and known as bioavailable fraction were decreased and the fractions of As in 3rd and 4th stages that correspond relatively non-liable fraction were increased. Such a stabilization of As shows that the abundant nano Fe° on the surface of INPBC mixed with As-contaminated soils played the co-precipitation of As leaching from soil by surface complexation with iron. The results of this study may imply that INPBC as a promising amendments for the stabilization of As-contaminated soil play an important role.

Differences in Structural Characteristics and Eu(III) Complexation for Molecular Size Fractionated Humic Acid (분자량별 분류에 따른 휴믹산의 구조적 특성 및 Eu(III)과의 착물 반응 특성 비교에 대한 연구)

  • Shin, Hyun-Sang;Rhee, Dong-Seok;Kang, Kihoon
    • Analytical Science and Technology
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    • v.14 no.2
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    • pp.159-166
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    • 2001
  • A humic acid(HA, Aldrich Co) sample was subjected to ultrafiltration for molecular size fractionation and three fractions of different nominal size($F_1$: 1,000-10,000 daltons; $F_2$: 10,000-50,000 daltons; $F_3$: 100,000-300,000 daltons) were obtained. The structural characteristics of the size-fractionated HA were analyzed using their IR and solid state C-13 NMR spectral data, and the carboxylate group contents of the humic acids were determined using their pH titration data. The $^7F_0-{^5}D_0$ excitation spectra of Eu(III) complexes of the size-fractionated mgHA in aqueous solution were acquired($[Eu(III)]=1.0{\times}10^{-4}mol\;L^{-1}$, $(HA)=470-970mg\;L^{-1}$) at pH 5.0 using a pulsed tunable laser system, in which metal binding properties of the size-fractionated HA were elucidated and compared on another. Characterization of the IR and C-13 NMR spectral data indicated that the fraction($F_3$) with molecules of larger size were primarily aliphatic, while the fractions($F_1$, $F_2$) with smaller molecules of less than 50,000 daltons were predominantly aromatic. Titration data were consistent with an increase in the number of carboxylate groups per unit mass as molecular size became smaller. The $^7F_0-{^5}D_0$ excitation spectral data of Eu(III)-humate complexes showed that the peak maxima on these spectra were shifted toward lower energies with increasing molecular size of HA, indicating the higher degree of bindings of the Eu in the molecules of larger size. We also discussed the relationship of the lower energy shifts of the maximum peaks with increasing the molecular size of HA with the structural differences of the size-fractionated HA.

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Comparison of Soil Physicochemical Properties According to the Sensitivity of Forest Soil to Acidification in the Republic of Korea (우리나라 산림토양의 산성화 민감도평가와 그에 따른 토양 이화학적 특성 비교분석)

  • Lee, Ah Lim;Koo, Namin
    • Journal of Korean Society of Forest Science
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    • v.109 no.2
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    • pp.157-168
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    • 2020
  • The sensitivity of forest soil to acidification in the Republic of Korea (ROK) was evaluated based on pHH2O, cation exchange capacity (CEC), and base saturation (BS). Sensitivity to acidification was categorized into three grades: adequate level (AL, pH ≧ 4.2, CEC ≧ 15cmol/kg, BS ≧ 15%), caution level (CL, at least one indicator is below AL), and severe Level (SL, all three indicators are below AL). Soil samples were collected from the 65 stationary monitoring plots (40 × 40 ㎢), distributed throughout ROK. Only 19% of soil samples were classified as AL, while 66% and 15% were CL and SL, respectively. The median of pHH2O, CEC, BS, and Ca/Al indicator in AL soils was pH 4.64, 20.7cmol/kg, 29%, and 6.3, respectively. Moreover, BCex (K+, Mg2+, Ca2+) and available phosphorus (AP) concentration compared with a threshold value and molar ratio of BCex and AP to total nitrogen (TN) was high. This indicates that AL soils have a good nutrient condition. The molar Ca/Al ratio, an indicator for toxicity of exchangeable aluminum (Alex), was more than 1, indicating no negative impact of Alex on plant growth. On the contrary, the median of pHH2O, CEC, and BS in SL soils was pH 4.02, 13.2cmol/kg, and 10%, respectively. The Ca/Al index was less than 0.6, which indicates that negative impacts of Alex on plants were high. Furthermore, both the concentration of BCex in SL soils and the BCex/TN ratio were the lowest among the three acidity degrees. This shows that SLsoils can be degraded by soil acidification compared with less acidic soils.

A Study on Fractionation and Characterization of Water-Soluble Natural Fe-Chelates From Garbage Compost and Activated Sewage Sludge (활성오니(活性汚泥) 및 진개퇴비중(塵芥堆肥中) 수용성(水溶性) 철(鐵) 킬레이트의 분리(分離)와 특성(特性)에 관(關)한 연구(硏究))

  • Park, Nae-Joung;Lindsay, W.L.
    • Applied Biological Chemistry
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    • v.18 no.4
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    • pp.194-202
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    • 1975
  • This study was conducted to study the properties of the water-soluble natural chelating agents from garbage compost and activated sewage sludge responsible for Fe chelation, which is closely associated with the effectiveness in correcting iron chlorosis in plant. The water-soluble fraction of these materials was fractionated by menas of Sephadex gel filtration and the fractions of Fe chehates were traced by radioactive $^{59}Fe$. The fractions were examined by ultraviolet and infrared. spectroscopy and stability constants for Fe. The water-soluble fraction from garbage compost was separated by Sephadex G-25 into approximately four fractions. Most of the added $^{59}Fe$ was associated with fraction I, which appeared at the void volume. Further fractionation by Sephadex G-50 indicated that the molecular weight of water-soluble chelating agents is in the approximate range of 5000 to 10,000. The water-soluble fraction from activated sewage sludge gave six fractions by Sephadex G-25. Most of the added $^{59}Fe$ was found in the fraction I,II, and III, The molecular weights of most chelating agents associated with $^{59}Fe$ appeared to be less than 5,000 and those of fraction I that appeared at the void volume was in the range of 5,000 to 1,000. Discrepancy between radio activity count and UV absorption indicated the heterogeneity of the fractions obtained by Sephadex gel filtration. Ultraviolet absorption spectra of all fractions separated by Sephadex G-25 and containing chelating agents showed no differences. Fraction IV and V of sewage extract showed absorption maxima and shifting similar to nucleic acid components suggesting the presence of decomposition products of nucleic acid. Similarity fraction VI contained phenolic type amino acid groups. Fraction I of compost extract contained most of the added $^{59}Fe$ and showed weak but extra definite absorption in the 1230, and $1270cm^{-1}$ region, suggesting that extra oxygen groups in polyphenolic structure were probably involved in Fe chelation. In sewage extract, fraction I,II, and III in which most of the $^{59}Fe$ was found, showed strong definite polypeptide absorption in the region of $1540cm^{-1}$ due to NH deformation and C-N stretching of amide groups in the peptidebond. These extra functional groups in fraction I, II, and III appeared to be associated with Fe chelation. The other fractions, not associated with $^{59}Fe$, still have carboxyl and hydroxyl groups, suggesting that these functional groups in these water extracts may not independently form the Fe chelates. Precipitation of ferric hydroxide precluded measuring the stability constants for Fe-chelates. However, the formation constants for Zn chelates as log K values for compost extract and sewage extract at pH 4.0 from which the strength of chelation with Fe could be presumed, were 8.23, and 9.75, respectively, indicating strong complexation with metals. The chelating capacity of compost extract containing 6.5 g organic matter per liter was 0.82 mM, and that of sewage extract containing 5.3 g per liter was 0. 64 mM.

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A study of Establishment on Radiomap that Utilizes the Mobile device Indoor Positioning DB based on Wi-Fi (Wi-Fi 기반 모바일 디바이스 실내측위 DB를 활용한 라디오맵 구축에 관한 연구)

  • Jeong, In Hun;Kim, Chong Mun;Choi, Yun Soo;Kim, Sang Bong;Lee, Yun
    • Journal of Korean Society for Geospatial Information Science
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    • v.22 no.3
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    • pp.57-69
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    • 2014
  • As of 2013, Korean population density is 505 persons per $1km^2$ and is ranked 3rd place in the most densely populated countries exception of city-states. It shows clearly the population is concentrated in the city area. To fulfil this urban concentration population demand, the enlargement and complexation of buildings, subway and other underground spaces connection tendency has been intensified, and it is need to construct the indoor spatial information DB as well as the accurate indoor surveying DB to promote people's safety and social welfare. In this study, Sadang station and Incheon National Airport were aimed for the construction of Wi-Fi AP location DB and RadioMap DB by collecting the indoor AP raw datas by using mobile device and those collected results were ran through the process of verification, supplementation, and analyzation. To evaluate the performance of constructed DB, 10 points in Incheon Airport- 3rd flr in block A, and 9 points in Sadang station-B1 were selected and calculated the estimated points and ran evaluation experiment using survey positioning error, which is distance between real position and the estimated position. The result shows that Incheon international airport's average and standard deviation was separately 17.81m, 17.79m and Sadang station's average and standard deviation was separately 22.64m, 23.74m. In Sadang station's case, the areas near the exit has low performance of surveying position due to fewer visible AP points than other areas. As total datas were examined except those position, it was verified that the user's location was mapping close position in surveying positioning by using constructed DB. It means that constructed DB contains correct Wi-Fi AP locations and radio wave patterns in object region, so it is considered that the indoor spatial information service based on constructed DB would be available.

Removal of Arsenite by Nanocrystalline Mackinawite(FeS)-Coated Alumina (나노크기 매킨나와이트로 코팅된 알루미나에 의한 아비산염의 제거)

  • Lee, Seungyeol;Kang, Jung Chun;Park, Minji;Yang, Kyounghee;Jeong, Hoon Young
    • Journal of the Mineralogical Society of Korea
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    • v.26 no.2
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    • pp.101-110
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    • 2013
  • Due to the large specific surface area and great reactivity toward environmental contaminants, nanocrystalline mackinawite (FeS) has been widely applied for the remediation of contaminated groundwater and soil. Furthermore, nanocrystalline FeS is rather thermodynamically stable against anoxic corrosion, and its reactivity can be regenerated continuously by the activity of sulfate-reducing bacteria. However, nanocrystalline mackinawite is prone to either spread out along the groundwater flow or cause pore clogging in aquifers by particle aggregation. Accordingly, this mineral should be modified for the application of permeable reactive barriers (PRBs). In this study, coating methods were investigated by which mackinawite nanoparticles were deposited on the surface of alumina or activated alumina. The amount of FeS coating was found to significantly vary with pH, with the highest amount occurring at pH ~6.9 for both minerals. At this pH, the surfaces of mackinawite and alumina (or activated alumina) were oppositely charged, with the resultant electrostatic attraction making the coating highly effective. At this pH, the coating amounts by alumina and activated alumina were 0.038 and 0.114 $mmol{\cdot}FeS/g$, respectively. Under anoxic conditions, arsenite sorption experiments were conducted with uncoated alumina, uncoated activated alumina, and both minerals coated with FeS at the optimal pH for comparison of their reactivity. Uncoated activated alumina showed the higher arsenite removal compared to uncoated alumina. Notably, the arsenite sorption capacity of activated alumina was little changed by the coating with FeS. This might be attributed to the abundance of highly reactive hydroxyl functional groups (${\equiv}$AlOH) on the surface of activated alumina, making the arsenite sorption by the coated FeS unnoticeable. In contrast, the arsenite sorption capacity of alumina was found to increase substantially by the FeS coating. This was due to the consumption of the surface hydroxyl functional groups on the alumina surface and the subsequent occurrence of As(III) sorption by the coated FeS. Alumina, on the surface area basis, has about 8 times higher FeS coating amount and higher As(III) sorption capacity than silica. This study indicates that alumina is a better candidate than silica for the coating of nanocrystalline mackinawite.

Reduction and Equilibrium of Vanadium-Diethylenetriamine Pentaacetates at Mercury Electrode in Aqueous Solution (수용액중의 수은전극에서 바나듐-디에틸렌트리아민 펜타아세트산염의 환원 및 평형연구)

  • Ki-Suk Jung;Se Chul Sohn;Young Kyung Ha;Tae Yoon Eom;Sock Sung Yun
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.55-64
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    • 1989
  • Reduction and equilibrium of vanadium-DTPA (DTPA = diethylenetriaminepentaacetic acid, $H_5A$) complexes at mercury electrodes are studied in 0.5M $NaClO_4$ aqueous solution at 3.2 < pH < 10.5 and 25$^{\circ}$C. At 3.2 < pH < 5.9, the reduction reaction is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}HA^{2-}$, while at 5.9 < pH < 10.5 it is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}A^{3-}$. The stability constants of $V{\cdot}HA^{2-}$ and $V{\cdot}A^{3-}$ are found to be $6.46{\times}10^{9}$ and $3.09{\times}10^{14}$, respectively. V(IV)-DTPA undergoes stepwise complexation as $VO^{2+}+H_2A^{3-}=VO{\cdot}HA^{2+}H^{+}$ and $VO{\cdot}HA^{2-}=VO{\cdot}A^{3+}+H$, where acidity constant of $VO{\cdot}HA^{2-}$- is pKa = 7.15. Stability constants of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $1.41{\times}10^{14}$ and $3.80{\times}10^{17}$, respectively. It is detected that $VO^{2+}-DATA$ is reduced irreversibly to $VO^{2-}$ with the transfer coefficient of $\alpha$ = 0.43. At more cathodic overpotential, the reduction is stepwise as V(IV)${\to}$V(III)${\to}$V(II). The first one corresponds to $VO{\cdot}HA^{2-}+e^{-}{\to}VO{\cdot}HA{3+}$ at 3.2 < pH < 7.2 and $VO{\cdot}A^{3-}+e^{-}{\to}VO{\cdot}A^{4-}$ at 7.2 < pH < 10.5. The second is identical to that of V(III). Diffusion coefficients of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $(9.0{\pm}0.3){\times}10^{-6}cm^2/s$ and $(5.9{\pm}0.4){\times}10^{-6}cm^2/ses$, respectively.

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