• 제목/요약/키워드: Cu+ complex

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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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The Spatial and Vertical Variations of Metal Pollution in Sediments after Tidal Power Plant Operation in Shihwa Lake (시화호 조력발전소 가동으로 인한 퇴적물 내 중금속 오염 특성 변화)

  • LEE, JIHYUN;JEONG, HYERYEONG;CHOI, JIN YOUNG;RA, KONGTAE
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.24 no.4
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    • pp.535-547
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    • 2019
  • In this study, the heavy metal analysis in sediments (surface sediments, sediments cores and settling particles) from Shihwa Lake has been carried out to evaluate the changes of metal pollution levels in sediments after the operation of Tidal Power Plant (TPP). The average concentrations of metals in surface sediments sampled in 2015 were 8% (Cd)~31% (Zn, Hg) lower than in 2009 before TPP operation. Results of calculating the pollution load index (PLI) with 8 metals, the PLI value in 2015 showed a 18% decrease compared to 2009. However, Cu, Zn, Pb concentrations of surface sediments in 2015 at the upper region around industrial complex still exceeded the TEL (threshold effect level) values for sediment quality guideline in Korea. After the operation of TPP, the metal contaminated depths were increasing from 15 cm to 30 cm at S6 site and from 8 cm to 20 cm at S7 site, respectively. Our data showed that the mean concentration of heavy metals in core samples decreased but the contaminated depth increased. The average of the total sedimentation flux for particulate matter increased by 3.2 times from 32.5 g/㎡/d in 2009 to 103.5 g/㎡/d in 2015. This showed that the bottom sediments were resuspended by the operation of TPP, resulting in an increase of particulate matter in the water column. These results suggest that the sediments contaminated with heavy metals seem to be resuspended and relocated due to the water current caused by the operation of TPP. Cr, Cu, Zn, Pb and Cd were highly exceeding the TEL values in the upstream region and accumulated more than 40 cm of sediment depth, indicating that heavy metal contamination through industrial activity were still a serious environmental problem of Shihwa Lake. Although the metal pollution of Shihwa Lake has been slightly reduced, the contaminated sediments with heavy metals inside of Shihwa Lake might be discharged to outer sea after the resuspension by TPP operation. It is necessary for the advanced scientific approach and political decision to drastically reduce the heavy metal pollution of the study region.

Uptake and Translocation of Heavy Metals to Rice Plant on Paddy Soils in "Top-Rice" Cultivation Areas (탑라이스 생산지역 논 토양 중 잔류중금속의 벼 흡수이행)

  • Park, Sang-Won;Yang, Ju-Seok;Ryu, Seung-Won;Kim, Dae-Yeon;Shin, Joung-Du;Kim, Won-Il;Choi, Ju-Hyeon;Kim, Sun-Lim;Saint, Andrew Flynn
    • Korean Journal of Environmental Agriculture
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    • v.28 no.2
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    • pp.131-138
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    • 2009
  • Heavy metal residues in soil, rice straw, unhulled rice, rice hull, polished rice, and rice barn on the rice paddy in the "Top rice production complex which is non-contaminated area were evaluated. It was observed that the average concentrations of As, Cd, Cu, Pb, and Hg in the paddy soils were 1.235, 0.094, 4.412, 4.728 and 0.0279 mg/kg, respectively. There were no cultivation areas exceeded of the threshold for soil contamination designated by "The Soil Environment Conservation Law" in Korea. For the polished rice, there were no samples exceeded of a permissible level of heavy metal residues such as 0.051 mg/kg of As, 0.040 mg/kg of Cd, 0.345 mg/kg of Cu, 0.065 mg/kg of Pb and 0.0015 mg/kg of Hg. For the uptake and translocation of heavy metals to rice plant, a main part of heavy metal accumulation was rice straw, and then rice bran. Furthermore, it shown that accumulation of heavy metals in unhulled rice, rice hulls, brown rice, and polished rice was approximately similar as low. The slopes of translocation of heavy metals from soil to polished rice were following order as Cd, 0.4321 > Cu, 0.054 ${\fallingdotseq}$ Hg, 0.052 > As, 0.021 > Pb, 0.008. It was observed that potential ability of Cd uptake in rice plant and then its translocation into polished rice was very high. Concentrations of copper and mercury absorbed in the rice plant were moderate for translocating into the polished rice, while the arsenic and lead in the plant were scarcely translocated into the polished rice. The distribution of heavy metals absorbed and translocated into aboveground parts of rice plant was appeared that there were remained at 63.3-93.4% in rice straw, 6.6-36.9% in unhulled rice, 0.6-5.7% in rice hulls, 3.2-31.3% in brown rice, 0.8-4.6% in rice bran and 1.1-26.7% in polished rice. The accumulation ratio of Cd in the aboveground parts of rice plant was remained at 26.7-31.3% in brown and polished rice.

Formation and Dissociation Kinetics of Zinc(II) Complexes of Tetraaza-Crown-Alkanoic Acids (Zinc(Ⅱ) Tetraaza-Crown-Allkanoic Acids 착물의 형성 및 해리 반응속도론)

  • Choi, Ki Young;Kim, Dong Won;Kim, Chang Suk;Park, Byung Bin;Choi, Suk Nam;Hong, Choon Pyo;Ryu, Hae Il
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.403-409
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    • 2000
  • The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

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Kinetic Studies of Reaction of Transion Metal Ion with Macrocyclic Ligands. Containing Nitrogen and Oxygen Donor Atoms (전이금속 이온과 Macrocyclic Ligand 사이의 반응에 관한 속도론적 연구 질소원자와 산소원자를 포함하는 거대고리 리간드를 중심으로)

  • Kim Jin-Ho;Cho Moon-Hwan;Hyeoun Dong-Ho;Park Hyu-Bum;Kim Si-Joong;Lee Ihn-Chong
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.418-423
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    • 1990
  • The protonation constants for the macrocyclic ligands 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloeicosane (NdienOdienH$_4$), 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa cycloheptadecane (NdienOenH$_4$), and 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloheptadecane (NenOdienH4) have been determined by the potentiometry in aqueous solutions (25$^{\circ}C$, I = 0.1, KNO$_3$). The stability constants for complexes formed in the aqueous solution (25$^{\circ}C$, I = 0.1, KNO$_3$) between the above ligands and the metal ions (Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)) have been measured by potentiometry. The rate of the ligand substitution reaction was measured spectrophotometrically by the addition of aqueous solutions of ethylenediamine to the solution of the complex. From the study of the temperature effect on the rate constant (k$_{obs}$), activation parameters (E$_a$,${\{Delta}H^{\neq}$, and ${\{Delta}S^{\neq}$) have been determined. The possible mechanism for the substitution reaction is proposed.

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A Study on the Runoff Characteristics and Water Quality Management of Seung-Gi Stream Area (승기천 유역의 오염물 유출특성 및 수질관리방안 연구)

  • Seo, Hyung-Joon;Chung, Sang-Won;Park, Mi-Ok;Lee, Byung-Ryul
    • Clean Technology
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    • v.7 no.4
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    • pp.251-263
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    • 2001
  • This study was conducted to provide a basic information for recovery plan of Seung-Gi Stream which is a major stream of Incheon metropolitan area. Source and characteristics of pollutants were analyzed and studied. Samples were taken 10 rounds in 5 sections in Seung-Gi stream. Annual pollutants loads and sectional characteristics of pollutants loads were investigated regarding flow rate, pH, DO, SS, $BOD_5$, $COD_{Cr}$, T-P, TKN and concentrations of Zn, Cd, Cu, Cr atoms which enter into Seung-Gi stream during rainy and dry season respectively. As one came close to the Nam-Dong Industrial Complex, sectional discharge loads were heavy and water quality was failed to meet the standard by "Environmental Standard of River Quality". As a result, heavy load of pollutants in Seung-Gi stream was considered to influence negatively the sea water quality of Incheon. Solution plans to solve problems are as follows. First, circulation of treated water at Seung-Gi WWTP(Wastewater Treatment Plant) and retreated water by URC(ultra rapid coagulation) process treat with that. Second, sewage and wastewater is gathered, make it disposed. After then, we circulate treated water. If solution plans be applied, we can predict water quality. Then we could grope for how make to recovery role of Seung-Gi stream as stream.

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Adhesion Properties between Polyimide Film and Copper by Ion Beam Treatment and Imidazole-Silane Compound (이온빔 및 이미다졸-실란 화합물에 의한 폴리이미드 필름과 구리의 접착 특성)

  • Kang, Hyung Dae;Kim, Hwa Jin;Lee, Jae Heung;Suh, Dong Hack;Hong, Young Taik
    • Journal of Adhesion and Interface
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    • v.8 no.1
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    • pp.15-27
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    • 2007
  • Polyimide (PI) surface modification was carried out by ion-beam treatment and silane-imidazole coupling agent to improve the adhesion between polyimide film and copper. Silane-imidazole coupling agent contains imidazole functional groups for the formation of a complex with copper metal through a coordination bonding and methoxy silane groups for the formation of siloxane polymers. The PI film surface was first treated by argon (Ar)/oxygen ($O_2$) ion-beam, followed by dipping it into a modified silane-imidazole coupling agent solution. The results of X-ray photoelectron spectroscopy (XPS) spectra revealed that the $Ar/O_2$ plasma treatment formed oxygen functional groups such as hydroxyl and carbonyl groups on the polyimide film surface and confirmed that the PI surface was modified by a coupling reaction with imidazole-silane coupling agent. Adhesion between copper and the treated PI film by ion-beam and coupling agent was superior to that with untreated PI film. In addition, adhesion of PI film treated by an $Ar/O_2$ plasma to copper was better than that of PI film treated by a coupling agent. The peeled-off layers from the copper-PI film joint were completely different in chemical composition each other. The layer of PI film side showed similar C1s, N1s, O1s spectra to the original Upilex-S and no Si and Cu atoms appeared. On the other hand the layer of copper side showed different C1s and N1s spectra from the original PI film and many Si and Cu atoms appeared. This indicates that the failure occurs at an interface between the imidazole-silane and PI film layers rather than within the PI layers.

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Copper(II) Sorption Mechanism on Kaolinite : An EPR and EXAFS Study (캐올리나이트 표면에서의 구리 수착 메카니즘 : 전자상자성공명 및 EXAFS 연구)

  • Sung Pil Hyun;Kim F Hayes
    • Journal of the Mineralogical Society of Korea
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    • v.17 no.1
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    • pp.1-9
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    • 2004
  • Copper(II) sorbed on kaolinite (KGa-lb) was studied using electron paramagnetic resonance (EPR) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The sorbed copper(II) had an isotropic EPR signal with $g_{iso}\;=\;2.19$ at room temperature. At 77 K, the isotropic signal converted to an axially symmetric anisotropic signal with $g_{\$\mid$}\;=\;2.40,\;g_{\bot}\;=\;2.08,\;and\;A_{\$\mid$}\;=\;131\;G$. These EPR results suggest that the sorbed copper(II) forms an outer-sphere surface complex with a tetragonally distorted $CuO_{6}$ octahedral structure on the kaolinite. In the sorption measurement, the amount of sorbed copper increased with increasing pH of the solution. However, the intensity of the isotropic EPR line was not directly proportional to the amount of sorbed copper. This discrepancy was resolved by assuming the formation of a surface precipitate at higher pH that is invisible by EPR. The EXAFS data confirmed the existence of the surface precipitate. The best fit for the EXAFS of the sorbed copper showed that each copper on the kaolinite had 6.8 copper neighbors located $3.08\;{\AA}$ from it, in addition to the first shell oxygen neighbors, including 4 equatorial O at $1.96\;{\AA}$ and 2 axial O at $2.31\;{\AA}$. This work shows that the local environment of the copper sorbed on the kaolinite changes as a function of pH and surface loading, and that the EPR and EXAFS are useful in studying such changes.

Assessment of Environmental Contaminant Levels in Water, Sediments and Adjacent Soils and Spider from Several Stream Sites in Korea (국내 하천들의 수질, 하천 퇴적물, 주변 토양 및 별늑대거미 체내 중금속 축적량을 통한 환경오염도 평가)

  • Byun, Sang-Hyuk;Ryoo, Keon-Sang;Choi, Jong-Ha;Kim, Yong-Gyun;Lee, Hwa-Sung
    • Journal of Environmental Science International
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    • v.17 no.3
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    • pp.287-296
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    • 2008
  • A comprehensive quality survey for heavy metals, organophosphorous and organochlorine residual pesticides, and coplanar PCBs in samples such as water, sediments and soils as well as spiders has been implemented. The samples were undertaken at nine stream sites and their vicinity in August 2006, representing different surrounding environments. The levels of PCBs were expressed as concentrations and WHO-TEFs. Among 12 coplanar PCBs as target compounds in this study, 2,3', 4,4', 5-PentaCB (IUPAC # 118) was the congener with the highest concentration. The total concentrations and TEF values of coplanar PCBs in Siheung stream sediment (heavy industrial complex site located in Ansan city) were 3915.50 pg/g and 0.8366 pg-TEQ/g on a dry weight basis, respectively. Such levels were around 40 times higher compared to sediment from Gapyung stream (green site located in the upper of Myunggi mountain). It is probably due to the direct input of PCBs trom PCBs treatment materials. Organophosphorous (EPN, dementon-s-methyl, diazinon, parathion, and phenthoate) and organochlorine (alpha-BHC, aldrin, 4,4'-DDT, 4,4'-DDE, endosulfan alpha and etc.) pesticides were not detected above 5 ppb of detection limits. The concentrations of Cu and Cd in water and sediment samples from Siheung stream were 44.11 and $0.17ug/m\ell$ and $713.42{\mu}g/g$ and $3.73{\mu}g/g$, respectively, which contained $20\sim40$ times higher concentrations than those from Gapyung stream. In addition to the water and sediment samples, the levels of heavy metals in spider from designated sampling sites were also determined. Heavy metals in spider collected near Siheung stream was appeared to be equivalent and/or a little higher levels with respect to other spiders. Furthermore, the ratio of relative heavy metals (Cu, Cd, and Pb) in spider from each stream site showed a correlation as similar as that of heavy metals in soil samples.

Effect of Soil Properties on Leaching of Preservative Components from CCA-treated Wood (토양 특성이 CCA 처리재로부터 방부제 성분의 용탈에 미치는 영향)

  • Jeong, Yong Gi;Kim, Gyu-Hyeok
    • Journal of the Korean Wood Science and Technology
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    • v.33 no.6 s.134
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    • pp.87-94
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    • 2005
  • This study was carried out to investigate the effect of soil types and soil properties on wood preservative leaching. Radiata pine (Pinus radiata Don.) sapwood stakes, which had been treated with 2.0%(w/v) CCA, were leached for 12 weeks by a common laboratory method in four different soils and for 14 days by the AWPA standard leaching method in water. The physical and chemical properties of the four soils were determined, and the percent leaching of the individual component of CCA was correlated with the various soil properties. The data show that leaching of preservative chemicals from treated wood exposed to soil is influenced by the type of soil. The preservative leaching was greater when wood was exposed to water than when the wood was in contact with water-saturated soil. The greatest chromium, copper and arsenic leaching from CCA-treated stakes were observed in the sandy loam, loam, and sand, respectively, and the least amount of leaching of CCA components occurred in the silty loam. The leaching of preservative components from treated wood is extremely complex and appears to be influenced differently by the soil properties. The extent of copper leaching from CCA treated wood appears to be related to exchangeable Mg and sum of bases. There is a reasonably good relationship between chromium leaching and exchangeable Mg, and between arsenic leaching and exchangeable K, soil Ni, Mn, Fe, Cr, or Cu content. Since this study was conducted based on laboratory leaching method using small cross-sectional dimensions; thus, data obtained from this experiment should not be used to predict leaching characteristics from commercial-size wood used in real situation. Accordingly, further studies are necessary using outdoor ground-contact leaching.