• Journal of Soil and Groundwater Environment
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• v.12 no.4
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• pp.16-24
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• 2007

An investigation on the polluted sediments in the Lake Sihwa and the benthos that inhabited on the sediments was conducted. Cost effective remediation alternatives were derived form the results of the investigation. The sediment samples taken from four sampling points out of thirteen showed relatively high heavy metal (particularly copper) concentrations which exceeded the Effects Range Low (ERL) of the National Oceanic and Atmospheric Administration, USA. The four sampling points were located in front of industrial complexes. Although the heavy metals appeared to have affected the growth of the benthos, the concentration of it did not exceed the criteria of dredging that were developed by Netherlands or the State of Washington, USA. However, contamination by organic matters and sulfur compounds was severe, which exceeded the criteria of dredging that were established in Japan. The sediments taken from the four sampling points which were contaminated with heavy metals showed higher organic matter content in general. The organic matters in the sediments depleted oxygen in summer, which appeared to be fatal to the benthos. A comprehensive analysis on the sediments, benthos, and other environmental impact from the contaminated sediments drew a conclusion that the benthonic environment of the Lake Sihwa needed a stepwise remediation, giving a particular emphasis on the clean up of the sediments upstram of the Lake which could cause odor problems to the nearby residential area.

• Korean Journal of Soil Science and Fertilizer
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• v.19 no.4
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• pp.307-314
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• 1986

Cu(II) binding mechanisms with water soluble organic fractions (WSOF) extracted from an agricultural soil (W), a soil treated with sludge for 6 years ($WS_6$), a sludge-soil mixture incubated for one week ($WS_1$), and sewage sludge (SS) were studied by electron spin resonance (ESR) spectroscopy and potentiometric titrations. Cu(II)-WSOF complexes produced $g_{11}$ values which were larger than $g_{\perp}$ values, indicating that the coordination of Cu(II) complex was an elongated octahedron. At liquid $N_2$ temperature (77K), the Cu(II)-W complex showed an anisotropic ESR spectrum while the Cu(II)-SS complex showed an isotropic spectrum. These spectral results suggest that the oxygen donor ligands of W may form relatively strong bonds with $Cu^{2+}$ due to extensive chelation while ligands of SS may form little or no chelate bonds with $Cu^{2+}$. The ESR spectra of Cu(II)-SS complex also suggest that each of four in-plane ligands (e.g., $COO^-$, $H_2O$, $Cl^-$, etc.) may act independently as monodentate ligands. Oxygen donor ligands such as aromatic carboxyl groups were probably the major Cu(II) binding sites in W. Sulfonate, aliphatic carboxyl group, and N-containing ligands were probably the major binding sites in SS at pH 5. The Cu(II) complexation with N-containing groups increased as sludge was added to the soil. Much higher (6x) pyridine concentrations were required to displace W from Cu(II)-W complex as compared to the Cu(II)-SS complex.

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.366-370
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• 1989

A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

• Korean Journal of Soil Science and Fertilizer
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• v.28 no.3
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• pp.207-217
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• 1995

Extracting efficiencies of seven extracting solutions currently employed in extracting heavy metals from soils were compared and the functional relationships among them were calculated by regression analysis for Cd, Zn, Cu, and Pb. Extracting solutions employed were 0.1M HCl, 0.1M $HNO_3$, 0.05M EDTA, 0.001M DTPA(pH 7.3), 1M $NH_4OAc$ (pH 7.0), 0.1M $NH_4Ox$, and 4M $HNO_3$ respectively. Soil samples were collected from rice paddy fields near old zinc mining sites and from rice paddy fields near agro-industry complexes. Soils sampled from old zinc mining sites were also extracted using a sequential extraction method. Extraction by 4M $HNO_3$ and sequential extraction were performed on the samples collected both in 1979 and in 1991 to investigate the change in content and in chemical form of heavy metals. Functional relationships among the extracting solutions were highly correlated for Cd and Zn, whereas those for Cu and Pb were not. The predominant chemical form of Cd. Zn, Cu, and Pb in soils from old zinc mining sites was found to be of sulfide/residue form. The exchangeable form of Cd, the organically bound form of Cu, and the carbonate form of Pb were relatively high, while the sulfide/residue form of Zn was very high(> 79%). Although transformation among the extracted forms was not clear during those 12 years, a decrease in total content of Cd, Zn, Cu, and Pb was clearly observed.

• Economic and Environmental Geology
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• v.28 no.4
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• pp.337-350
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• 1995

The Hwacheon-ri mineralized area is located within the Cretaceous Gyeongsang Basin of the Korean peninsula. The mineralized area includes the Hwacheon, Daeweon, Kuryong and Cheongryong mines. Each of these mines occurs along copper-bearing hydrothermal quartz veins that crosscut late Cretaceous volcanic rocks, although some disseminated ores in host rocks also exist locally. Mineralization can be separated into three distinct stages (I, II, and III) which developed along preexisting fracture zones. Stage I is ore-bearing, whereas stages II and III are barren. The main phase of ore mineralization, stage I, can be classified into three substages (Ia, Ib and Ic) based on ore mineral assemblages and textures. Substage Ia is characterized by pyrite-arsenopyrite-molybdenite-pyrrhotite assemblage and is most common at the Hwacheon deposit. Substage Ib is represented by main precipitation of Cu, Zn, and Pb minerals. Substage Ic is characteristic of hematite occurrence and is shown only at the Kuryong and Cheongryong deposits. Some differences in the ore mineralization at each mine in the area suggest that the evolution of hydrothermal fluids in the area varied in space (both vertically and horizontally) with respect to igneous rocks relating the ore mineralization. Fluid inclusion data show that stage I ore mineralization mainly occurred at temperatures between ${\approx}350^{\circ}$ and ${\approx}200^{\circ}C$ from fluids with salinities between 9.2 and 0.5 wt.% eq. NaCl. In the waning period of substage Ia, the high temperature and salinity fluid gave way to progressively cooler, more dilute fluids of later substage Ib and Ic (down to $200^{\circ}C$, 0 wt.% NaCl). There is a systematic decrease in the calculated ${\delta}^{18}O_{H2O}$ values with paragenetic time in the Hwacheon-ri hydrothermal system from values of ${\approx}2.7$‰ for substage Ia, through ${\approx}-2.8$‰ for substage Ib, to ${\approx}-9.9$‰ for substage Ic. The ${\delta}D$ values of fluid inclusion water also decrease with decreasing temperature (except for the Daeweon deposit) from -62‰ (substage Ia) to -80‰ (substage Ic and stage III). These trends are interpreted to indicate the progressive cooler, more oxidizing unexchanged meteoric water inundation of an initial hydrothermal system which is composed of highly exchanged meteoric water. Equilibrium thermodynamic interpretation of the mineral assemblages with the variation in amounts of chalcopyrite through the paragenetic time, and the evolution of the Hwacheon-ri hydrothermal fluids indicate that the solubility of copper chloride complexes in the hydrothermal system was mainly controlled by the variation of temperature and $fo_2$ conditions.

• Korean Journal of Environmental Agriculture
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• v.12 no.1
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• pp.51-57
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• 1993

Objective of this research was to assess the influence of reaction time on the heavy metal-organic ligand complexation by employing kinetic models. Aqueous solutions of humic (HA) or fulvic acid (FA) were reacted with metal solutions with 1:1 ratio to form complexes. Efficiency of organic ligand on metal removal was determined by separating the precipitates from solution using $0.45\;{\mu}m$ filter paper. Complexation between Cu or Pb and HA or FA followed the first- or multiple first order kinetics, largely depending on metal concentration and kind of organic ligand. Amounts of precipitates were increased proportionally with reaction time but reached to quasiequilibrium where rate of precipitate formation was not varied with time. Copper-ligand complexation was, irrespective of ligand, fitted to the single first order kinetics at Cu concentrations lower than $300{\mu}M$, but this was fitted to the multiple first order kinetics at Cu concentrations higher than $300{\mu}M$. As increasing Cu concentrations, the precipitates formed more readily, judging from the increased rate constants (${\kappa}$). In the multiple first order kinetics, ${\kappa}$ was decreased as reaction steps proceeded. Most of Cu-ligand precipitates were formed within 15 min. FA precipitated Cu more rapidly than HA did. ${\kappa}$ for Pb-HA complexation was decreased but that for Pb-FA reaction was increased, as increasing Pb concentration. Most of Pb-organic ligand complexation occurred within 30 min. Afterwards, ${\kappa}$ values were relatively small and not affected much by time. Pb was precipitated by humic acid more readily than Cu when metal concnetrations were $200{\sim}300{\mu}M$. However, when metal concentrations were in the ranges of $400{\sim}500{\mu}M$, a reversed tendency was observed.

• Analytical Science and Technology
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• v.9 no.4
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• pp.336-344
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• 1996

The extraction of trace cobalt, copper, nickel, cadmium, lead and zinc in urine samples of organic and alkali metal matrix into chloroform by the complex with a dithizone was studied for graphite furnace AAS determination. Various experimental conditions such as the pretreatment of urine, the pH of sample solution, and dithizone concentration in a solvent were optimized for the effective extraction, and some essential conditions were also studied for the back-extraction and digestion as well. All organic materials in 100 mL urine were destructed by the digestion with conc. $HNO_3$ 30 mL and 30% $H_2O_2$ 50 mL. Here, $H_2O_2$ was added dropwise with each 5.0 mL, serially. Analytes were extracted into 15.0 mL chloroform of 0.1% dithizone from the digested urine at pH 8.0 by shaking for 90 minutes. The pH was adjusted with a commercial buffer solution. Among analytes, cadmium, lead and zinc were back-extracted to 10.00 mL of 0.2 M $HNO_3$ from the solvent for the determination, and after the organic solvent was evaporated, others were dissolved with $HNO_3-H_2O_2$ and diluted to 10.00 mL with a deionized water. Synthetic digested urines were used to obtain optimum conditions and to plot calibration-eurves. Average recoveries of 77 to 109% for each element were obtained in sample solutions in which given amounts of analytes were added, and detection limits were Cd 0.09, Pb 0.59, Zn 0.18, Co 0.24, Cu 1.3 and Ni 1.7 ng/mL, respectively. It was concluded that this method could be applied for the determination of heavy elements in urine samples without any interferences of organic materials and major alkaline elements.