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Sequential Extraction of Heavy Metals in Soils and A Case Study (토양중의 중금속 연속추출방법과 사례연구)

  • Jung, Myung Chae
    • Economic and Environmental Geology
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    • v.27 no.5
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    • pp.469-477
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    • 1994
  • Many researchers have investigated most representative sequential extraction method using various reagents for determining the chemical forms of metals in soils and sediments. In this paper, a newly modified method for sequential extraction scheme based on Tessier's method by Environmental Geochemistry Research, Centre for Environmental Technology, Imperial College, was introduced and examined. In comparison with Tessier's method, originally designed for sediment analysis by Atomic Absorption Spectrophotometry (AAS), the sequential extraction scheme has been developed for the multi-element analysis by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The partitioning of particulate trace elements was classified into five fractions: (i) exchangeable, (ii) bound to carbonates or specially adsorbed, (iii) bound to Fe and Mn oxides, (iv) bound to organic matter and sulphides and (v) residuals. The experimental results of the pilot study for in-house reference material (HRM2) and certified international standard reference material (SRM2711) using the modified method showed not only reasonable precision and accuracy but also acceptable overall recovery rates. In addition, mine dump soils sampled in the Dalsung Cu-W mine, Korea were prepared and sequentially extracted using the method. Most of Cu was bound to organic matter/sulphides and residual fractions. The dominant fraction of soil Pb and Zn in the study area was found in the residuals. The fraction of Cd showed a wide variation between samples and could be found bound to the carbonates or specially adsorbed, oxides, organic fraction and residuals. The recovery rates of Cd, however, were poor due to relatively low Cd concentrations in soils. The heavy metals in these mine dumps appear to be in the more inert forms and should not be readily bioavailable. The soils, however, had very low pH values (average 4.1) and had sandy textures; consequently, rapid infiltration of rainfall may increase leaching of Zn and Cd which were found to be around 5 to 10% of the exchangeable fraction. As a result of the investigation of this study, it has been strongly recommended that these mine waste materials should still be considered a significant contaminant source and will need environmental remediation to prevent pollutants from being released into the environment.

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Evaluation of Sequential Extraction Techniques for Selected Heavy Metal Speciation in Contaminated Soils

  • Lee, Jin-Ho;Doolittle, James J.;Oh, Byung-Taek
    • Korean Journal of Environmental Agriculture
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    • v.25 no.3
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    • pp.236-246
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    • 2006
  • In this study, we give insight into questionable results that can be encountered in the conventional sequential extraction of heavy metals (Cd, Cu, and Zn) from soils. Objectives of this study were to determine the extraction variability of exchangeable (EXC)-metals as using six different EXC-extractants commonly accepted, and to investigate selectivity problems with carbonates bound (CAB)-metal fraction, a buffered acetate (1.0 M NaOAc; pH 5.0) extractable-metal fraction, leading to erratic results in especially non-calcareous soils. The contents of EXC-metals were markedly varied with the different extractability of various EXC-metal extractants used. The contents of EXC-Cd fraction were ranged from 2.0 to 74.3% of total Cd content in all of the metal spiked soils studied. The contents of EXC-Zn fraction extracted with the different EXC-extractants were varied with soil types, which were from 0.4 to 3.9% of total Zn in the calcareous soils, from 7.6 to 17.9% in the acidic soil, and from 13.6 to 56.8% in the peat soil. However, the contents of EXC-Cu fraction were relatively similar among the applications of different EXC-meal extractants, 0.2 to 2.1 % of total Cu, in all soils tested. Also, these varied amounts of EXC-metal fractions, especially Cd and Zn, seriously impacted the contents of subsequent metal fractions in the procedure. Furthermore, the CAB-Cd, -Cu, and -Zn fractions extracted by the buffered acetate solution were in critical problem. That is, the buffered acetate solution dissolved not only CAB-metals but also metals that bound or occupied to subsequent fractions, especially OXD-metal fraction, in both calcareous and non-calcareous soils. The erratic results of CAB-fraction also seriously impacted the amounts of subsequent metal fractions. Therefore, the conventional sequential extraction should be reconsidered theoretically and experimentally to quantify the target metal fractions or might be progressively discarded.

Space-time-dissociated differential sedimentation and its relationship with the rate of relative sea-level change: the Lower Ordovician Mungok Formation, Korea

  • Choi Yong Seok;Lee Yong Il
    • 한국석유지질학회:학술대회논문집
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    • autumn
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    • pp.14-30
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    • 2000
  • Hierarchically controlled sequence stratigraphic analysis shows that the Lower Ordovician mixed carbonate-siliciclastic Mungok Formation, Korea consists of three depositional sequences: T1, T2, and T3. Sequence boundaries are generally marked by abrupt transition from coarse-grained shallow-water carbonates to fine-grained deeper-water carbonates mixed with fine-grained siliciclastics, and show indication of subaerial exposure such as karstification. Within this sequence stratigraphic framework, facies characteristics indicate that the Mungok sequences were mostly deposited in subtidal ramp environments. High-frequency cycles consist of upward-shallowing facies successions. Cycles of shallow-water and basinal deposits are not represented well, probably due to cycle amalgamation. Cycle stacking patterns do not show a consistent thickness change that reflects a large-scale sea-level change due to unfilled accommodation space. The Mungok sequences show that many factors including relative sea-level change and topography are involved in controlling sequence development on carbonate ramps. The depositional setting evolved from the high-energy ramps in the sequences T1 and T2 into the low-energy ramp in the sequence T3. Topography is interpreted to have been responsible for the different energy regimes of the carbonate ramps in the Mungok sequences. The high ramp gradient in the sequences T1 and T2 seems to be caused by space-time-dissociated differential sedimentation resulting in spatially narrow distribution of sediment filling, which in turn may be related to high rate of relative sea-level change. In contrast, low ramp gradient was maintained in the sequence T3 during slow changes of relative sea level resulting in broad distribution of sediment filling.

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Alkaline Hydrolysis of Y-Substituted Phenyl Phenyl Thionocarbonates: Effect of Changing Electrophilic Center from C=O to C=S on Reactivity and Mechanism

  • Kim, Song-I;Park, Hey-Ran;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.179-182
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    • 2011
  • Second-order rate constants ($k_{OH^-}$) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with $OH^-$ in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The $k_{OH^-}$ values for the reactions of 4a-i have been compared with those reported previously for the corresponding reactions of Y-substituted phenyl phenyl carbonates (3a-i) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and mechanism. Thionocarbonates 4a-i are less reactive than the corresponding carbonates 3a-i although 4a-i are expected to be more reactive than 3a-i. The Bronsted-type plot for reactions of 4a-i is linear with $\beta_{lg}$ = -0.33, a typical $\beta_{lg}$ value for reactions reported to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step (RDS). Furthermore, the Hammett plot correlated with $\sigma^o$ constants results in much better linearity than that correlated with $\sigma^-$ constants, indicating that expulsion of the leaving group is not advanced in the RDS. Thus, alkaline hydrolysis of 4a-i has been concluded to proceed through a stepwise mechanism with formation of an intermediate being RDS, which is in contrast to the forced concerted mechanism reported for the corresponding reactions of 3a-i. Enhanced stability of the intermediate upon modification of the electrophilic center from C=O to C=S has been concluded to be responsible for the contrasting mechanisms.

Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Butane-2,3-dione Monoximate and 4-Chlorophenoxide: Origin of the α-Effect

  • Kim, Min-Young;Min, Se-Won;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.49-53
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    • 2013
  • Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

The Effects of Carbonate Minerals in Gully-pot Sediment on the Leaching Behavior of Heavy Metals Under Acidified Environment (우수관퇴적물에 함유된 탄산염광물이 산성환경에서의 중금속 용출거동에 미치는 영향 평가)

  • 이평구;유연희
    • Economic and Environmental Geology
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    • v.35 no.3
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    • pp.257-271
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    • 2002
  • One of the main interests in relation to heavily contaminated gully-pot sediment in urban area is the short term mobility of heavy metals, which depends on the pH of acidic rainwater and on the buffering effects of carbonate minerals. The buffering effects of carbonates are determined by titration (acid addition). Leaching experiments are carried out in solutions with variable initial HN03 contents for 24h. The gully-pot sediment appears to be predominantly buffered by calcite and dolomite. In case of sediment samples, which highly contain carbonates, pH decreases more slowly with increasing acidity. On the other hand, for the sediment samples, which less contain carbonate minerals, pH rapidly drops until it reaches about 2 then it decreases slowly. The leaching reactions are delayed until more acid is added to compensate for the buffering effects of carbonates. The Zn, Cu, Pb and Mn concentrations of leachate rapidly increase with decreased pH, while Cd, Co, Ni, Cr and Fe dissolutions are very slow and limited. The solubility of heavy metals depends not only on thc pH values of leachatc but also on the speciation in which metals are associated with sediment particles. In slightly to moderately acid conditions, Zn, Cd, Co, Ni and Cu dissolutions become increasingly important. As deduced from leaching runs, the relative mobility of heavy metals at pH of 5 is found to be: Zn > Cd > Co > Ni > Cu » Pb > Cr, suggesting that moderately acid rainwater leach Zn, Cd, Co, Ni and Cu from thc contaminated gully-pot sediment, while Pb and Cr would remain fixed. The buffering effects of Ca- and Mg-carbonates play an important role in delaying as well as limiting the leaching reactions of heavy metals from highly contaminated gully-pot sediment. The extent of such a secondary environmental pollution will thus depends on how well the metals in sediment can be leached by somewhat acidic rain water. Changes in the physicochemical environments may result in the severe environmental pollution of heavy metals. These results are to be taken into account in the management of contaminated sediments during rainstorms.

Adsorption of Ruthenium on the alkaline Earth Metal Compounds (알카리토금속 화합물에 의한 루테늄의 흡착)

  • 류경옥;문세기;이근범
    • Journal of the Korean Ceramic Society
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    • v.19 no.2
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    • pp.145-151
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    • 1982
  • Many materials such as silica gel, metallic oxide, activated alumina and alkaline earth metal carbonates were employed as filter media for gaseous oxides of ruthenium volatilized during high level radioactive waste processing. The adsorption efficiency of ruthenium on these materials was evaluated. For the purpose of observing behavior of ruthenium oxides, thermogravimetric analysis of ruthenium oxide in a stream of oxygen was carried out. The rate of volatilization was proportional to the square root of oxygen partial pressure, and increased exponentially with temperature. At $650^{\circ}C$, gaseous ruthenium oxides showed a strongly marked effect of deposition. Of all the materials available, calcium oxide proved to be the best that could be used to adsorb ruthenium.

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Synthesis of Cyclic Carbonates under Supercritical Condition (초임계상에서 고리형 카보네이트의 합성)

  • Yoo, Jin-Yi;Jun, Joon-Ho;Sung, Un-Gyung;Lee, Yoon-Bae
    • Proceedings of the KAIS Fall Conference
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    • 2007.05a
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    • pp.264-266
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    • 2007
  • 지구의 온난화를 가속시키는데 일조하고 있는 이산화탄소($CO_{2}$)와 Epoxy를 Tetrabutylammonium bromide를 촉매로 하여 초임계 상태에서 반응시켜 2차 전지의 전해질 물질로 사용 가능한 4-ethyl-l,3-dioxolan-2-one, 4-methyl-1,3-dioxlan-2-one, 4-phenyl-1,3-dioxolan-2-one, 4-Chloromethyl-1,3-dioxolan-2-one을 합성하여 $^{l}H-NMR$을 이용하여 분석하였다.

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Study on the Stability of Ascorbic acid in several Antacid Preparations (분말성제제(粉末性製劑)의 안정성(安定性)에 관(關)한 연구(硏究) -수종제산제중(數種制酸劑中)의 Ascorbic acid의 안정성(安定性)에 관(關)한 연구(硏究)-)

  • Shin, Sang-Chul;Lee, Min-Hwa;Woo, Chong-Hak
    • Journal of Pharmaceutical Investigation
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    • v.3 no.1_2
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    • pp.34-50
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    • 1973
  • There are many reports on the stability of drugs in powders and tablets. The stabilities of ascorbic acid in the antacid preparations, such as calcium carbonate, magnesium carbonate, magnesium trisilicate, magnesium alumino silicate, and dried aluminum hydroxide gel under various humidities were examined. From the result of the experiment, it was assumed that the concentration of ascorbic acid, the amount of water-vapor sorption, and the physical character of the antacid ingredients were the main factors, influencing the degradation of ascorbic acid. The ascorbic acid, mixed with carbonates, such as calcium carbonate, was degradaded rapidly, while the preparation with dried aluminum hydroxide gel was slightly degraded after 10 days. A 2% ascorbic acid in the prepation was rapidly degraded than 10% ascorbic acid in the preparation.

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Synthesis of High Tc Superconductor YBa2Cu3O7-$\delta$ by Oxalate Coprecipitation Method I. Theoretical Considerations based on Analytical Chemistry (옥살레이트 공침전법에 의한 고온 초전도체 YBa2Cu3O7-$\delta$의 합성 I. 분석화학적 측면의 이론적 고찰)

  • 김배환;김배연;김창은;최진호
    • Journal of the Korean Ceramic Society
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    • v.26 no.1
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    • pp.91-99
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    • 1989
  • The concentrations of hydroxide, carbonate and oxalate for Y(III), Ba(II) and Cu(II) ions in an aqueous solution have been theoretically calcuated with respect to pH and their solubility diagram could be obtained. The optimum pH ofr oxalate coprecipitates at room temperature was estimated as<4, which was not influenced by carbonates and hydroxides in H2O solvent. The yield is dependent on the concentration of added oxalic acid, but the concentration of oxalic acid was fixed as 0.1M in this calculation for simplicity.

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