• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.879-888
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• 1992

Separation of the optical isomers of free amino acids by a reversed phase high performance liquid chromatography has been studied by adding a copper(II) complex of L-proline or L-proline derivatives (hydroxy-L-proline, N-benzyl-L-proline, p-xylenyl-L-proline, p-xylenyl-hydroxy-L-proline) in the mobile phase. An OPA postcolumn detection system was used for the detection of amino acids. The chromatographic properties for the free amino acids were discussed in terms of the pH, the kinds and concentration of chelate or organic modifier. The retention behaviors of the free amino acids were considerably different from, those of DNS-amino acids or DABS-amino acids. The enantioselectivity of the free amino acids was better than that of derivatized amino acids. The enantioselectivity between the optical isomers observed by use of the Cu(II)-p-xylenyl-L-proline chiral cheleate was the best among the several copper(II) chelate. A separation mechanism could be illustrated not only by the hydrophobic interaction of the diastereomer with stationary phase but also by the steric effect of the ligand exchange reaction between the free-amino acids and copper chelate.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.401-405
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• 2010

The Schiff base 1,2-bis(E-2-hydroxy benzylidene amino)anthracene-9,10-dione has been synthesized and explored as ionophore for preparing PVC-based membrane sensors selective to the copper ($Cu^{2+}$) ion. Potentiometric investigations indicate high affinity of these receptors for copper ion. The best performance was shown by the membrane of composition (w/w) of ionophore: 1 mg, PVC: 33 mg, DOP: 66 mg and KTpClPB as additive were added 50 mol % relative to the ionophore in 1 ml THF. The proposed sensor's detection limit is $2.8{\times}10^{-7}$ M over pH 5 at room temperature (Nernstian slope 31.76 mV/dec.) with a response time of 15 seconds and showed good selectivity to copper ion over a number of interfering cations.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.341-346
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• 1996

Electrochemical determination of iodide was carried out by stripping voltammetry with a $(Cin)Cu(NO_3)_2$ modified-carbon paste electrode. Iodide was coordinated onto the electrode surface containing $(Cin)Cu(NO_3)_2$ via ion exchange. The oxidation peak potential of incorporated iodide was ＋0.72 V. The optimum analytical conditions for the determination of iodide were investigated using linear sweep voltammetry. Optimum conditions for the electrochemical determination of iodide were as follows: i) A predeposition solution was 0.1 M $KNO_3.$ ii) The deposition time was 10 min. iii) The composition of the electrode was 40% (w/w). The detection limit for iodide was $1.0{\times}10^{-6}M$ and the relative standard deviation was ${\pm}5.5%\;in\;2.0{\times}10^{-5}M$(four repetitions). The interference effect of other anions were also investigated. $Cl^-,\;Br^-,\;C_2O_4^{2-},\;and\;ClO_4^-$ ions do not interfere for the determination of iodide. When $SCN^-$ was added to the deposition solution, the oxidation peak current of iodide ion was decreased roughly 32%.

• Economic and Environmental Geology
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• v.29 no.2
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• pp.139-150
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• 1996

The Yucheon Bi deposits at Cheongha, Gyeongsangbugdo, is of a middle Paleogene (49 Ma) vein type, and is hosted in sandstone and shale of Banyawal formation in Cretaceous age. Based on mineral paragenesis, vein structure and mineral assemblages, two minera1ization stages were distinguished. The stage I consists of quartz with small amount of chlorite, pyrite, epidote, hal1oysite, vermiculite, serpentine and rutile associated with sericitization. The stage II is characterized by Bi minera1ization such as bismuthinite, Bi-Cu-Pb-S mineral, tetradymite, native gold, pyrite, pyrrhotite, arsenopyrite, wolframite, rutile, hematite, sphalerite, chalcopyrite, galena with alteration of sericite, chlorite, K-feldspar, albite and epidote. Fluid inclusion data indicate that fluid temperature and NaCl equivalent wt.% salinity range from 431 to $150^{\circ}C$ and from 19.2 to 0.18wt.% in the stage II. Evidence of boiling during the base-metal minera1ization indicates pressures 241 to 260 bars. Sulfur fugacity($-log\;f_{S2}$) deduced by mineral assemblages and compositions ranges from 5.1 to 5.7atm in early stage, from > 8.4 atm in middle stage and from 13.5 to 19.3 atm in late stage. It suggests that complex histories of progressive coo1ing, dilution and boiling were occurred by the mixing of the fluids. The ${\delta}^{34}S$, ${\delta}^{18}O$ and ${\delta}D$ data range from 2.5 to 3.9%, -0.5 to -4.1% and -29.7 to -47%, respectively. It indicated that hydrothermal fluids may be magmatic origin with boiling and mixing of meteoric water increasing paragenetic time.

• Economic and Environmental Geology
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• v.30 no.4
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• pp.289-301
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• 1997

The Boguk cobalt mine is located within the Cretaceous Gyeongsang Sedimentary Basin. Major ore minerals including cobalt-bearing minerals (loellingite, cobaltite, and glaucodot) and Co-bearing arsenopyrite occur together with base-metal sulfides (pyrrhotite, chalcopyrite, pyrite, sphalerite, etc.) and minor amounts of oxides (magnetite and hematite) within fracture-filling $quartz{\pm}actinolite{\pm}carbonate$ veins. These veins are developed within an epicrustal micrographic granite stock which intrudes the Konchonri Formation (mainly of shale). Radiometric date of the granite (85.98 Ma) indicates a Late Cretaceous age for granite emplacement and associated cobalt mineralization. The vein mineralogy is relatively complex and changes with time: cobalt-bearing minerals with actinolite, carbonates, and quartz gangues (stages I and II) ${\rightarrow}$ base-metal sulfides, gold, and Fe oxides with quartz gangues (stage III) ${\rightarrow}$ barren carbonates (stages IV and V). The common occurrence of high-temperature minerals (cobalt-bearing minerals, molybdenite and actinolite) with low-temperature minerals (base-metal sulfides, gold and carbonates) in veins indicates a xenothermal condition of the hydrothermal mineralization. High enrichment of Co in the granite (avg. 50.90 ppm) indicates the magmatic hydrothermal derivation of cobalt from this cooling granite stock, whereas higher amounts of Cu and Zn in the Konchonri Formation shale suggest their derivations largely from shale. The decrease in temperature of hydrothermal fluids with a concomitant increase in fugacity of oxygen with time (for cobalt deposition in stages I and II, $T=560^{\circ}C-390^{\circ}C$ and log $fO_2=$ >-32.7 to -30.7 atm at $350^{\circ}C$; for base-metal sulfide deposition in stage III, $T=380^{\circ}-345^{\circ}C$ and log $fO_2={\geq}-30.7$ atm at $350^{\circ}C$) indicates a transition of the hydrothermal system from a magmatic-water domination toward a less-evolved meteoric-water domination. Sulfur isotope data of stage II sulfide minerals evidence that early, Co-bearing hydrothermal fluids derived originally from an igneous source with a ${\delta}^{34}S_{{\Sigma}S}$ value near 3 to 5‰. The remarkable increase in ${\delta}^{34}S_{H2S}$ values of hydrothermal fluids with time from cobalt deposition in stage II (3-5‰) to base-metal sulfide deposition in stage III (up to about 20‰) also indicates the change of the hydrothermal system toward the meteoric water domination, which resulted in the leaching-out and concentration of isotopically heavier sulfur (sedimentary sulfates), base metals (Cu, Zn, etc.) and gold from surrounding sedimentary rocks during the huge, meteoric water circulation. We suggest that without the formation of the later, meteoric water circulation extensively through surrounding sedimentary rocks the Boguk cobalt deposits would be simple veins only with actinolite + quartz + cobalt-bearing minerals. Furthermore, the formation of the meteoric water circulation after the culmination of a magmatic hydrothermal system resulted in the common occurrence of high-temperature minerals with later, lower-temperature minerals, resulting in a xenothermal feature of the mineralization.

• 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.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.25 no.3
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• pp.380-391
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• 2015

Objectives: The objective of this study is to assess airborne particulate matter pollution and its effect on health of residents living near Ansim Briquette Fuel Complex and its vicinities. Also, this study measured and analyzed the concentration of TSP, $PM_{10}$, $PM_{2.5}$, and heavy metals which influences on the environmental and respiratory disease in Ansim Briquette Fuel Complex, Daegu, Korea. Methods: In this study, we analyzed various environmental pollutants such as particulate matter and heavy metals from Ansim Briquette Fuel Complex that adversely affected local residents's health. In particular, we verified the concentration distribution and characteristics of exposure for TSP, $PM_{10}$, and $PM_{2.5}$ among particulate matters, and heavy metals(Cd, Cr, Cu, Mn, Ni, Pb, Fe, Zn, and Mg). In that regard, the official test method on air pollution in Korea for analysis of particulate matter and heavy metal in atmosphere were conducted. The large capacity air sampling method by the official test method on air pollution in Korea were applied for sampling of heavy metals in atmosphere. In addition, we evaluated the concentration of seasonal environmental pollutants for each point of residence in Ansim Briquette Fuel Complex and surrounding area. The sampling measured periods for air pollutants were from August 11, 2013 to February 21, 2014. Furthermore, we measured and analyzed the seasonal concentrations(summer, autumn and winter). Results: The average concentration for TSP, $PM_{10}$, and $PM_{2.5}$ by direct influence area at Ansim Briquette Fuel Complex were 1.7, 1.4 and 1.9 times higher than reference region. In analysis results of seasonal concentrations for particulate matter in four direct influence and reference area, concentration levels for winter were generally somewhat higher than concentrations for summer and autumn. The average concentrations for Cd, Cr, Mn, Ni, Pb, Fe, and Zn in direct influence area at Ansim Briquette Fuel Complex were $0.0008{\pm}0.0004{\mu}g/Sm^3$, $0.0141{\pm}0.0163{\mu}g/Sm^3$, $0.0248{\pm}0.0059{\mu}g/Sm^3$, $0.0026{\pm}0.0011{\mu}g/Sm^3$, $0.0272{\pm}0.0084{\mu}g/Sm^3$, $0.4855{\pm}0.1862{\mu}g/Sm^3$, and $0.3068{\pm}0.0631{\mu}g/Sm^3$, respectively. In particularly, the average concentrations for Cd, Cr, Mn, Ni, Pb, Fe, and Zn in direct influence area at Ansim Briquette Fuel Complex were 1.9, 3.6, 2.1, 1.9, 1.4, 2.6, and 1.2 times higher than reference area, respectively. The continuous monitoring and management were required for some heavy metals such as Cr and Ni. Moreover, the average concentration in winter for particulate matter in direct influence area at Ansim Briquette Fuel Complex were generally higher than concentrations in summer and autumn. Also, average concentrations for TSP, $PM_{10}$, and $PM_{2.5}$ were from 1.5 to 2.0 times, 1.2 to 1.8 times, and 1.1 to 2.3 times higher than reference area, respectively. In results for seasonal atmospheric environment, TSP, $PM_{10}$, $PM_{2.5}$, and heavy metal concentrations in direct influence area were higher than reference area. Especially, the concentrations in C station were a high level in comparison with other area. Conclusions: In the results, some particulate matters and heavy metals were relatively high concentration, in order to understand the environmental pollution level and health effect in surrounding area at Ansim Briquette Fuel Complex. The concentration of some heavy metals emitted from direct influence area at Ansim Briquette Fuel Complex were relatively higher than reference area. In particular, average concentration for heavy metals in this study were higher than average concentrations in air quality monitoring station for heavy metal for 7 years in Deagu metropolitan region. Especially, the residents near Ansim Briquette Fuel Complex may be exposed to the pollutants(TSP, $PM_{10}$, $PM_{2.5}$, and heavy metals, etc) emitted from the factories in Ansim Briquette Fuel Complex.

• 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.

• 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.

• Analytical Science and Technology
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• v.9 no.3
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• pp.279-291
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• 1996

The new chelating resins, XAD-2, 4, 16-TAC and XAD-2, 4, 16-TAO were synthesized by Amberlite XAD-2, XAD-4, and XAD-16 macroreticular resins with 2-(2-thiazolylazo)-p-cresol(TAC) and 4-(2-thiazolylazo)orcinol(TAO) as functional groups and were characterized by elemental analysis and FT-IR spectrometry. It was found that the content of functional group in chelating resin was 0.60mmol/g in XAD-16-TAC and 0.68mmol/g in XAD-16-TAO respectively. The chelating resins were stable in acidic and alkaline solution and can be reused over 10 times. The sorption behavior of some metalions to two chelating resins was investigated by batch method, which included batch equilibrium, effect of pH, coexisting ions and masking agent. For the optimum condition of sorption, the time required for equilibrium was about 1 hour and optimum pH was 5. In the presence of anions such as ${SO_4}^{2-}$ and $CH_3COO^-$, the sorption of U(VI) ion was slightly reduced but other anions such as $Cl^-$ and $NO{_3}^-$ revealed no interference effect. Also, sorption capacity of U(VI) ion was decreased by addition of $CO{_3}^{2-}$ ion because of complex formation of $[UO_2(CO_3)_3]^{4-}$, but alkali metals and alkali earth metals including Na(I), K(I), Mg(II), and Ca(II) were not affected for the sorption extent. Masking agent, NTA showed better separation efficiency of U(VI) ion from coexisting metal ions such as Th(IV), Zr(IV), Hf(IV), Cu(II), Cd(II), Pb(II), Ni(II), Zn(II) and Mn(II) than EDTA, CDTA.