• Title/Summary/Keyword: Zn-complexes

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Geochemical Characteristics of Intertidal Surface Sediments along the Southwestern Coast of Korea (한국 서해남부 조간대 표층 퇴적물의 지화학적 특성)

  • Hwang, Dong-Woon;Ryu, Sang-Ok;Kim, Seong-Gil;Choi, Ok-In;Kim, Seong-Soo;Koh, Byoung-Seol
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.43 no.2
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    • pp.146-158
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    • 2010
  • In order to evaluate the characteristics of sediments and pollution by organic matter and metallic elements in intertidal sediments along the southwestern coast of Korea, we measured various geochemical parameters, including the mean grain size (Mz), water content (WC), ignition loss (IL), chemical oxygen demand (COD), acid volatile sulfide (AVS), and metallic elements (Al, Fe, Cu, Pb, Zn, Cd, Cr, Mn, Hg, As), in intertidal surface sediments. The Mz of the surface sediments ranged from 2.1 to 8.3$\phi$, indicating that the surface sediments consist of various sedimentary facies, such as sand, slightly gravelly mud, sandy mud, and silt. The IL and COD in surface sediment ranged from 0.8 to 5.5% (mean $2.9\pm1.2%$) and from 3.9 to $13.8\;mgO_2/g{\cdot}dry$ (mean $8.5\pm2.6\;mgO_2/g{\cdot}dry$), respectively, which were lower than the values for surface sediment in areas near fish and shellfish farms or industrial complexes. No AVS was detected at any sampling station, despite various sedimentary facies. Most of metallic elements in surface sediments showed relatively good positive correlations with Mz and IL, which imply that the concentrations of metallic elements are mainly controlled by grain size and the organic matter content. The concentrations of metallic elements, except As, at some stations were considerably lower than those in the Sediment Quality Guideline (Effect Range Low, ERL) proposed by the National Oceanic and Atmospheric Administration (NOAA) in the United States. Similarly, the geoaccumulation index (Igeo) class indicated that pollution by metallic elements in intertidal surface sediment, except As, was moderate or non-existent. Our results imply that the intertidal surface sediments along the southwestern coast of Korea are not polluted by organic matter and metallic elements and are healthy for benthic organisms.

Effects of Ionic strength and Anion species on Heavy Metal Adsorption by Zeolite (Ionic Strength 및 공존(共存) 음(陰)Ion이 Zeolite에 의(依)한 중금속(重金屬)의 흡착(吸着)에 미치는 영향(影響))

  • Lee, Jyung-Jae;Park, Byoung-Yoon;Choi, Jyung
    • Korean Journal of Environmental Agriculture
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    • v.7 no.2
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    • pp.96-101
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    • 1988
  • It is important to assess the effects of ionic strength and type of anions when studying the adsorption of heavy metals on zeolite because the background salt may complex with heavy metals and compete for adsorption sites. This experiment was carried out to determine the effect of ionic strength and anion species($Cl^-$, $SO^{2-}\;_4$, and $ClO^-\;_4$) on heavy metal adsorption. Heavy metal adsorption by zeolite from solutions in the range of 10 to 50ppm was studied in the presence of NaCl, $Na_2SO_4$ and $NaClO_4$, with different concentrations. The ionic strength ranged from 0.01 to 1.00. Adsorption of heavy metal cations could be described by the Freundlich isotherm equation. Increasing the ionic strength of equilibrium solutions, the amounts of heavy metal adsorbed on the zeolite surfaces decreased in all three of the anion systems. This fact could be attributed to the competition of background salt cation and the decrease in initial activity of heavy metal cations. In the presence of Cl anion, less adsorption resulted than in the presence of $SO_4$ or $ClO_4$ anions of the same ionic strength, indicating the presence of uncharged and negatively charged complexes of heavy metal with Cl ligands.

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Studies on Solvent Extraction and Analytical Application of Metal-dithizone Complexes(I). Separation and Determination of Trace Heavy Metals in Urine (Dithizone 금속착물의 용매추출 및 분석적 응용(제1보). 뇨중 흔적량 중금속 원소의 분리 정량)

  • Jeon, Moon-Kyo;Choi, Jong-Moon;Kim, Young-Sang
    • 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.

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Synthesis of Heptadentate Nitrogen-Oxygen Ligands (N4O3) with Substituting Groups and Determination of Stability Constants of Their Transition Metal(II) Complexes (치환기를 가진 일곱 자리 질소-산소(N4O3)계 리간드 합성과 전이금속(II) 이온 착물의 안정도상수 결정)

  • Kim, Sun-Deuk;Lee, Do-Hyub;Seol, Jong-Min
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.541-550
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    • 2010
  • A new $N_4O_3$ heptadentate ligand, N,N'-Bis(2-hydroxybenzyl)-1,3-bis[(2-aminoethyl)amino]-2-propanol(H-BAP 4HCl)was synthesized. The hydrochloric acid salts of Br-BAP 4HCl, Cl-BAP 4HCl, $CH_3O$-BAP 4HCl and $CH_3$-BAP 4HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_{3^-}$ groups at the para-site of the phenol group of the H-BAP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The elemental stepwise protonation constants(${logK_n}^H$) of the synthesized $N_4O_3$ ligands showed six steps of the proton dissociation. The orders of the overall dissociation constants($log{\beta}_p$) of the ligands were Br-BAP < Cl-BAP < H-BAP < $CH_3O$-BAP < $CH_3$-BAP. The orders agreed well with that of Hammett substituent constants($\sigma_p$). The calculated stability constants($logK_{ML}$) between the ligands and transition metal ions agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in Hammestt substituent constants($\sigma_p$). The order of the stability constants between the transition metal ions with the ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

A study on drainage characteristics and load amount evaluation by crop type in a hydroponic cultivation facility of horticultural complex (수경재배 시설원예단지 작물 유형별 배액 특성 및 부하량 평가 연구)

  • Jin, Yujeong;Kang, Taegyoung;Lim, Ryugab;Kim, Hyunwoo;Kang, Donghyeon;Park, Minjung;Son, Jinkwan
    • Journal of Wetlands Research
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    • v.23 no.4
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    • pp.352-363
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    • 2021
  • The purpose of this study was to evaluate the load of nutrients contained in the drainage discharged from the facility horticultural complex and to use them for re-use of fluids and design for introduction of water treatment plants. Representative hydroponic cultivation crops were selected as tomato, paprika, cucumber, and strawberry, and the total number of samples analyzed for water quality was 80. As a result of the analysis, since various fertilizer components such as N, P, K+, Na+, Mg2+, Ca2+, Si4+, HCO3-, Cl-, S2-, Fe, Mn, Cu, Zn, Mo and B are contained at very high concentrations in the drainage, the need for water treatment was confirmed. Through statistical analysis, it was analyzed that the drainage concentration of strawberries was lower than that of tomatoes, paprika, and cucumbers. In the case of tomatoes, these essential ion concentrations are the highest, so it was confirmed that they are subject to valuable resources in terms of reuse of fertilizers. The load of N and P of the drainage discharged from the facility horticultural complex 1m2 was analyzed. For N, the daily processing capacity of 4.0 kg of tomatoes, 3.3 kg of paprika, 3.0 kg of cucumbers, and 1.5 kg of strawberries was calculated based on 1 ha. It was suggested that the P concentration needs a scale and capacity that can handle 0.5 kg of tomatoes, 0.6 kg of paprika, 0.4 kg of cucumber, and 0.2 kg of strawberries per day. Through this study, the amount of nitrogen and phosphorus contained in the drainage discharged from the greenhouse of each crop was evaluated to analyze the economy. In addition, it was expected to be used as basic data that can be used to calculate the treatment capacity to be reflected when introducing water treatment facilities in facility horticultural complexes for sustainable agriculture.

Mineralogy and Geochemistry of the Jeonheung and Oksan Pb-Zn-Cu Deposits, Euiseong Area (의성(義城)지역 전흥(田興) 및 옥산(玉山) 열수(熱水) 연(鉛)-아연(亞鉛)-동(銅) 광상(鑛床)에 관한 광물학적(鑛物學的)·지화학적(地化學的) 연구(硏究))

  • Choi, Seon-Gyu;Lee, Jae-Ho;Yun, Seong-Taek;So, Chil-Sup
    • Economic and Environmental Geology
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    • v.25 no.4
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    • pp.417-433
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    • 1992
  • Lead-zinc-copper deposits of the Jeonheung and the Oksan mines around Euiseong area occur as hydrothermal quartz and calcite veins that crosscut Cretaceous sedimentary rocks of the Gyeongsang Basin. The mineralization occurred in three distinct stages (I, II, and III): (I) quartz-sulfides-sulfosalts-hematite mineralization stage; (II) barren quartz-fluorite stage; and (III) barren calcite stage. Stage I ore minerals comprise pyrite, chalcopyrite, sphalerite, galena and Pb-Ag-Bi-Sb sulfosalts. Mineralogies of the two mines are different, and arsenopyrite, pyrrhotite, tetrahedrite and iron-rich (up to 21 mole % FeS) sphalerite are restricted to the Oksan mine. A K-Ar radiometric dating for sericite indicates that the Pb-Zn-Cu deposits of the Euiseong area were formed during late Cretaceous age ($62.3{\pm}2.8Ma$), likely associated with a subvolcanic activity related to the volcanic complex in the nearby Geumseongsan Caldera and the ubiquitous felsite dykes. Stage I mineralization occurred at temperatures between > $380^{\circ}C$ and $240^{\circ}C$ from fluids with salinities between 6.3 and 0.7 equiv. wt. % NaCl. The chalcopyrite deposition occurred mostly at higher temperatures of > $300^{\circ}C$. Fluid inclusion data indicate that the Pb-Zn-Cu ore mineralization resulted from a complex history of boiling, cooling and dilution of ore fluids. The mineralization at Jeonheung resulted mainly from cooling and dilution by an influx of cooler meteoric waters, whereas the mineralization at Oksan was largely due to fluid boiling. Evidence of fluid boiling suggests that pressures decreased from about 210 bars to 80 bars. This corresponds to a depth of about 900 m in a hydrothermal system that changed from lithostatic (closed) toward hydrostatic (open) conditions. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S=2.9{\sim}9.6$ per mil) indicate that the ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids was ${\approx}8.6$ per mil. This ${\delta}^{34}S_{{\Sigma}S}$ value is likely consistent with an igneous sulfur mixed with sulfates (?) in surrounding sedimentary rocks. Measured and calculated hydrogen and oxygen isotope values of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values. Equilibrium thermodynamic interpretation indicates that the temperature versus $fs_2$ variation of stage I ore fluids differed between the two mines as follows: the $fs_2$ of ore fluids at Jeonheung changed with decreasing temperature constantly near the pyrite-hematite-magnetite sulfidation curve, whereas those at Oksan changed from the pyrite-pyrrhotite sulfidation state towards the pyrite-hematite-magnetite state. The shift in minerals precipitated during stage I also reflects a concomitant $fo_2$ increase, probably due to mixing of ore fluids with cooler, more oxidizing meteoric waters. Thermodynamic consideration of copper solubility suggests that the ore-forming fluids cooled through boiling at Oksan and mixing with less-evolved meteoric waters at Jeonheung, and that this cooling was the main cause of copper deposition through destabilization of copper chloride complexes.

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Geochemistry and Genesis of Hydrothermal Cu Deposits in the Gyeongsang Basin, Korea : Hwacheon-ri Mineralized Area (경상분지내 열수동광상의 지화학 및 성인연구 : 화천리지역 광화대)

  • So, Chil-Sup;Choi, Sang-Hoon;Yun, Seong-Taek
    • 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.

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