• Journal of Wetlands Research
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• v.25 no.4
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• pp.306-314
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• 2023

Stream sediments are an important component of water quality management because they are receptors of various pollutants such as heavy metals and organic matters emitted from upland sources and can be secondary pollution sources, adversely affecting water environment. To effectively manage the stream sediments, identification of primary sources of sediment contamination and source-associated control strategies will be required. We evaluated the performance of machine learning models in identifying primary sources of sediment contamination based on the physico-chemical properties of stream sediments. A total of 356 stream sediment data sets of 18 quality parameters including 10 heavy metal species(Cd, Cu, Pb, Ni, As, Zn, Cr, Hg, Li, and Al), 3 soil parameters(clay, silt, and sand fractions), and 5 water quality parameters(water content, loss on ignition, total organic carbon, total nitrogen, and total phosphorous) were collected near abandoned metal mines and industrial complexes across the four major river basins in Korea. Two machine learning algorithms, linear discriminant analysis (LDA) and support vector machine (SVM) classifiers were used to classify the sediments into four cases of different combinations of the sampling period and locations (i.e., mine in dry season, mine in wet season, industrial complex in dry season, and　industrial complex in wet season). Both models showed good performance in the classification, with SVM outperformed LDA; the accuracy values of LDA and SVM were 79.5% and 88.1%, respectively. An SVM ensemble model was used for multi-label classification of the multiple contamination sources inlcuding landuses in the upland areas within 1 km radius from the sampling sites. The results showed that the multi-label classifier was comparable performance with sinlgle-label SVM in classifying mines and industrial complexes, but was less accurate in classifying dominant land uses (50~60%). The poor performance of the multi-label SVM is likely due to the overfitting caused by small data sets compared to the complexity of the model. A larger data set might increase the performance of the machine learning models in identifying contamination sources.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.418-429
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• 2011

Novel chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), and zirconyl(II) complexes of $N^1,N^2$-bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide ($H_4L$, 1) have been synthesized and characterized by elemental, physical, and spectral analyses. The spectral data showed that the ligand behaves as either neutral tridentate ligand as in complexes 2-5 with the general formula $[H_4LMX_2(H_2O)]{\cdot}nH_2O$ (M=Cu(II), Ni(II), Co(II), X = Cl or $NO_3$), neutral hexadentate ligand as in complexes 10-12 with the general formula $[H_4LM_2Cl_6]{\cdot}nH_2O$ (M=Fe(III), Cr(III) or Ru(III)), or dibasic hexadentate ligand as in complexes 6-9 with the general formula $[H_2LM_2Cl_2(H_2O)_4]{\cdot}nH_2O$ (M = Cu(II), Ni(II), Co(II) or Mn(II), and 13 with general formula $[H_4L(ZrO)_2Cl_2]{\cdot}8H_2O$. Molar conductance in DMF solution indicated the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complexes 2, 5, and 6 showed $g_{\parallel}$ >g> $g_e$, indicating distorted octahedral structure and the presence of the unpaired electron in the $N^1,N^2$ orbital with significant covalent bond character. For the dimeric copper(II) complex $[H_2LCu_2Cl_2(H_2O)_4]{\cdot}3H_2O$ (6), the distance between the two copper centers was calculated using field zero splitting parameter for the parallel component that was estimated from the ESR spectrum. The antibacterial and antifungal activities of the compounds showed that, some of metal complexes exhibited a greater inhibitory effect than standard drug as tetracycline (bacteria) and Amphotricene B (fungi).

• 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.24 no.2
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• pp.106-116
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• 2005

This experiment was conducted to investigate available extraction capacity and potential mobility of heavy metal according to the distribution property and contamination level of heavy metals in soils and to suggest a reform measure of soil environment assessment methodology applied with soil quality and the official soil heavy metal test methods in domestic and foreign countries. The soils were collected from the natural forest paddy with long-term application of same type fertilizer, and paddies near metal mine and industrial complex. The post-treatment methods of soil were partial extraction, acid digestion and sequential extraction methods. For the heavy metal contents with different soil properties, it was shown that their natural forest and paddy soil were slightly low and similar to the general paddy soil, while their paddies near metal mine and industrial complex were higher than the standard level of Soil Environment Protection Act. Heavy metal concentrations in the soils with different soil properties had difference between $HNO_3\;and\;HNO_3+HCl$ extractant by US-EPA 3051a method. There were highly significant positive relationships in both two methods. It was appeared that the higher extractable concentration ratio with 0.1N-HCl to total heavy metal content with $HNO_3+HCl$ extractant the greater total heavy metal content. There were highly significant positive correlationship between total heavy metal content and extractable content with 0.1N-HCl. For extractable capacity of soil extractable solution compared to the total heavy metal content it was appeared that it extractable method with 0.1N-HCl was higher than those with EDTA and DTPA. In extractable ratio with 0.1N-HCl in the contaminated paddy soils near mine and industrial complex, it was shown that the lower soil pH, the higher total heavy metal content. The order of a potential mobility coefficient by distribution of heavy metal content with ie different typies in the soil was Cd>Ni>Zn>Cu>Pb. It could be known that contamination characteristics of heavy metals with different types of soils were affected by different heavy metal components, contamination degree and soil chemical properties, and heavy metal concentration with different extractable methods had great variations with adjacent environment. To be compared with assessment methodology of soil environment impact at domestic and foreign countries with our results, it might be considered that there was necessary to make a single analysis method based on total heavy metal content with environmental overloading concept because of various analysis methods for total heavy metal content and present analysis method with great variation according to soil environment. In spite of showing higher concentration of heavy metal with acidic digestion than the extractable method, it might be considered that there is need to be adjusted the national standard of soil heavy metal contamination.

• Conservation Science in Museum
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• v.24
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• pp.1-16
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• 2020

This paper presents the process of re-conservation and the results of research on the production method of the Iron Sword with Ring Pommel with Three-Pointed Leaf Decoration, one of the excavation findings from Tomb No. 55 in the Dalseong Ancient Tomb Complex in Daegu. This iron sword is a double weapon with two large swords housed within a single sheath. Four smaller swords are attached to the surface of the sheath, two on the upper portion and the other two below. It is the only such two-in-one weapon excavated intact thus far from an ancient Korean tomb. The records show that it underwent conservation treatment twice in the past. In this study, it was subjected to conservation treatment again to replace the stiffener in some cracking areas, and its material, composition, and production method were analyzed by CT, XRF analysis, and stereoscopic microscopy. The sword is mainly made of copper, but the golden component contains both gold and mercury, which suggests that the copper was plated in gold using mercury amalgamation. The examination of the production methods indicates that it was intended more to demonstrate the authority of its owner rather than to serve any practical use. The two upper small swords on the sheath were made in the same manner as the main swords, and the two small lower swords were cut from a single metal sheet. The sheath was made by cutting two metal sheets. Supports were used to attach the two small swords to the upper portion of the sheath, while the lower portion of the sheath was slit to allow the other two small swords to be inserted into it. The ring pommels of the main swords have a three-pointed leaf decoration. As for the other designs, the handle of the main sword features a series of semicircles, the decorative bands on the sheath have waves in dots, and the fish tail of the sheath shows diagonal lines of dots.

• 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.

• Economic and Environmental Geology
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• v.36 no.2
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• pp.75-87
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• 2003

The Haman-Gunbuk mineralized area is located within the Cretaceous Gyeongsang Basin along the southeastern part of the Korean peninsula. Major ore minerals, magnetite, scheelite, molybdenite and chalcopyrite, together with base-metal sulfides and minor sulfosalts, occur in fissure-filling tourmaline, quartz and carbonates veins contained within Cretaceous sedimentary and volcanic rocks anu/or granodiorite (118{\pm}$3.0 Ma). The ore and gangue mineral paragenesis can be divided into three distinct stages: Stage 1, tourmaline+quartz+Fe-Cu ore mineralization; Stage II, quartz+sulfides+sulfosalts+carbonates; Stage 111, barren calcite. Earliest fluids are recorded in stage I and early por-tions of stage II veins as hypersaline (35~70 equiv. wt.% NaCl+KCl) and vapor-rich inclusions which homogenize from ~30$0^{\circ}C$ to $\geq$50$0^{\circ}C$. The high-salinity fluids are complex chloride brines with significant concentrations of sodium, potassium, iron, copper, and sulfur, though sulfide minerals are not associated with the early mineral assemblage produced by this fluid. Later solutions circulated through newly formed fractures and reopened veins, and are recorded as lower-salinity(less than ~20 equiv. wt.% NaCl) fluid inclusions which homogenize primarily from ~200 to 40$0^{\circ}C$. The oxygen and hydrogen isotopic compositions of fluid in the Haman-Gunbuk hydrothermal system represents a progressive shift from magmatic-hydrothermal dominance during early mineralization stage toward meteoric-hydrothermal dominance during late mineralization stage. The earliest hydrothermal fiuids to circu-late within the granodiorite stock localiring the ore body at Haman-Gunbuk could have exsolved from the crystal-lizing magma and unmixed into hypersaline liquid and $H_2O$-NaCl vapor. As these magmatic fluids moved throughfractures, tourmaline and early Fe, W, Mo, Cu ore mineralization occurred without concomitant deposition of othersulfides and sulfosalts. Later solutions of dominantly meteoric origin progressively formed hypogene copper and base-metal sulfides, and sulfosalt 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 Environmental Impact Assessment
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• v.29 no.3
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• pp.157-181
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• 2020

Sediments from rivers, lakes and marine ports serve as end points for pollutants discharged into the water, and at the same time serve as sources of pollutants that are continuously released into the water. Until now, the contaminated sediments have been landfilled or dumped at sea. Landfilling, however, was expensive and dumping at sea was completely banned due to the London Convention. Therefore, this study applied contaminated sedimentation soil of 'Royal Palace Livestock Complex' as soil purification method. Soil remediation methods were applied to pretreatment, composting, soil washing, electrokinetics, and thermal desorption by selecting overseas application cases and domestically applicable application technologies. As a result of surveying the site for pollutant characteristics, Disolved Oxigen (DO), Suspended Solid (SS), Chemical Oxygen Demand (COD), Total Nitrogen (TN), and Total Phosphorus (TP) exceeded the discharged water quality standard, and especially SS, COD, TN, and TP exceeded the standard several tens to several hundred times. Soil showed high concentrations of copper and zinc, which promote the growth of pig feed, and cadmium exceeded 1 standard of Soil Environment Conservation Act. In the pretreatment technology, hydrocyclone was used for particle size separation, and the fine soil was separated by more than 80%. Composting was performed on organic and Total Petroleum Hydrocarbon (TPH) contaminated soils. TPH was treated within the standard of concern, and E. coli was analyzed to be high in organic matter, and the fertilizer specification was satisfied by applying the optimum composting conditions at 70℃, but the organic matter content was lower than the fertilizer specification. As a result of continuous washing test, Cd has 5 levels of residual material in fine soil. Cu and Zn were mostly composed of ion exchange properties (stage 1), carbonates (stage 2), and iron / manganese oxides (stage 3), which facilitate easy separation of contamination. As a result of applying acid dissolution and multi-stage washing step by step, hydrochloric acid, 1.0M, 1: 3, 200rpm, 60min was analyzed as the optimal washing factor. Most of the contaminated sediments were found to satisfy the Soil Environmental Conservation Act's standards. Therefore, as a result of the applicability test of this study, soil with high heavy metal contamination was used as aggregate by applying soil cleaning after pre-treatment. It was possible to verify that it was efficient to use organic and oil-contaminated soil as compost Maturity after exterminating contaminants and E. coli by applying composting.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.179-189
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• 2002

The Geology of the Shizhuyuan W-Sn-Bi-Mo deposits, situated 16 Ian southeast of Chengzhou City, Hunan Province, China, consist of Proterozoic metasedimentary rocks, Devonian carbonate rocks, Jurassic granitic rocks, Cretaceous granite porphyry and ultramafic dykes. The Shizhuyuan polymetallic deposits were associated with medium- to coarse-grained biotite granite of stage I. According to occurrences of ore body, ore minerals and assemblages, they might be classified into three stages such as skarn, greisen and hydrothernlal stages. The skarn is mainly calcic skarn, which develops around the Qianlishan granite, and consists of garnet, pyroxene, vesuvianite, wollastonite, amphibolite, fluorite, epidote, calcite, scheelite, wolframite, bismuthinite, molybdenite, cassiterite, native bismuth, unidetified Bi- Te-S system mineral, magnetite, and hematite. The greisen was related to residual fluid of medium- to coarse-grained biotite granite, and is classified into planar and vein types. It is composed of quartz, feldspar, muscovite, chlorite, tourmaline, topaz, apatite, beryl, scheelite, wolframite, bismuthinite, molybdenite, cassiterite, native bismuth, unknown uranium mineral, unknown REE mineral, pyrite, magnetite, and chalcopyrite with minor hematite. The hydrothermal stage was related to Cretaceous porphyry, and consist of quartz, pyrite and chalcopyrite. Scheelite shows a zonal texture, and higher MoO) content as 9.17% in central part. Wolframite is WO); 71.20 to 77.37 wt.%, FeO; 9.37 to 18.40 wt.%, MnO; 8.17 to 15.31 wt.% and CaO; 0.01 to 4.82 wt.%. FeO contents of cassiterite are 0.49 to 4.75 wt.%, and show higher contents (4.]7 to 4.75 wt.%) in skarn stage (Stage I). Te and Se contents of native bismuth range from 0.00 to 1.06 wt.% and from 0.00 to 0.57 wt.%, respectively. Unidentified Bi-Te-S system mineral is Bi; 78.62 to 80.75 wt.%, Te; 12.26 to 14.76 wt.%, Cu; 0.00 to 0.42 wt.%, S; 5.68 to 6.84 wt.%, Se; 0.44 to 0.78 wt.%.