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Mineralogical and chemical characterization of arsenic solid phases in weath-ered mine tailings and their leaching potential (풍화광미내 고상 비소의 광물학적${\cdot}$화학적 특성 및 용출 가능성 평가)

  • 안주성;김주용;전철민;문희수
    • Economic and Environmental Geology
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    • v.36 no.1
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    • pp.27-38
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    • 2003
  • Arsenic contamination around Au-Ag mining areas occurs mainly from the oxidation of arsenopyrite which is frequently contained in mine tailings. In weathered tailings, oxidation of sulfide minerals typically results in the formation of abundant ferric (oxy)hydroxides or (oxy)hydroxysulfates near the tailings surface, and arsenic may be associated with these secondary precipitates. In this study, solid phases of arsenic in weathered tailings of some Au-Ag mines were investigated through the SEM/EDS and sequential extraction analyses. The stability of As solid phases and the leaching potential were assessed with the variation of pH and Eh conditions. Oxidation of sulfides in the tailings samples was indicated by depletion of S molar concentrations compared to As and heavy metals. Under XRD examinations, jarosite as an Fe-oxyhydroxysulfate was found in the tailings of Deokeum, Dongil and Dadeok, and scorodite as an As-bearing crystalline mineral was identified from Dadeok which has the highest concentration of As (4.36 wt.%). Beudantite-like phases and some Pb-arsenates were also found under SEM/EDS analysis, and most of As phases were associated with Fe-(oxy)hydroxides and (oxy)hydroxysulfates despite a few arsenopyrite from Samgwang and Gubong. Sequential extraction analysis also showed that As was present predominantly as coprecipitated with Fe hydroxides from Dongil, Dadeok and Myungbong (72∼99%), and as sulfides (58%) and Fe hydroxide-associated forms (40%) from Samgwang and Gubong. In the tailings leaching experiment, As was released with high amounts by the dissolution of As-bearing Fe(oxy)hydroxysulfates in the lowest pH (2.7) conditions of Deokeum, and by desorption under alkaline conditions of Samgwang and Gubong. Higher leaching rates of arsenite(+3) were found under acidic conditions, which pose a higher risk to water quality. Changes in pH and Eh conditions coupled with microbial processes could influence the stabilities of the As solid phases, and thus, time amendments or landfilling of weathered tailings may result in enhanced As mobilization.

Characterization of Arsenic Immobilization in the Myungbong Mine Tailing (명봉광산의 광미 내 비소의 고정화 특성 연구)

  • Lee, Woo-Chun;Jeong, Jong-Ok;Kim, Ju-Yong;Kim, Soon-Oh
    • Economic and Environmental Geology
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    • v.43 no.2
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    • pp.137-148
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    • 2010
  • The Myoungbong mine located in Boseong-gun, Jellanamdo consists of Au-Ag bearing quartz veins which filled the fissures of Bulguksa granitic rocks of Cretaceous. The tailings obtained from the Myungbong mine were used to investigate the effects of various processes, such as oxidation of primary sulfides and formation(alteration) of secondary and/or tertiary minerals, on arsenic immobilization in tailings. This study was conducted via both mineralogical and chemical methods. Mineralogical methods used included gravity and magnetic separation, ultrasonic cleaning, and instrumental analyses(X-ray diffractometry, energy-dispersive spectroscopy, and electron probe microanalyzer) and aqua regia extraction technique for soils was applied to determine the elemental concentrations in the tailings. Iron (oxy)hydroxides formed as a result of oxidation of tailings were identified as three specific forms. The first form filled in rims and fissures of primary pyrites. The second one precipitated and coated the surfaces of gangue minerals and the final form was altered into yukonites. Initially, large amounts of acid-generating minerals, such as pyrite and arsenopyrite, might make the rapid progress of oxidation reactions, and lots of secondary minerals including iron (oxy)hydroxides and scorodite were formed. The rate of pH decrease in tailings diminished, in addition, as the exposure time of tailings to oxidation environments was prolonged and the acid-generating minerals were depleted. Rather, it is speculated that the pH of tailings increased, as the contribution of pH neutralization reactions by calcite contained in surrounding parental rocks became larger. The stability of secondary minerals, such as scorodite, were deteriorated due to the increase in pH, and finally arsenic might be leached out. Subsequently, calcimn and arsenic ions dissociated from calcites and scorodites were locally concentrated, and yukonite could be grown tertiarily. It is confirmed that this tertiary yukonite which is one of arsenate minerals and contains arsenic in high level plays a crucial role in immobilizing arsenic in tailings. In addition to immobilization of arsenic in yukonites, the results indicate that a huge amount of iron (oxy)hydroxides formed by weathering of pyrite which is one of typical primary minerals in tailings can strongly control arsenic behavior as well. Consequently, this study elucidates that through a sequence of various processes, arsenic which was leached out as a result of weathering of primary minerals, such as arsenopyrite, and/or redissolved from secondary minerals, such as scorodite, might be immobilized by various sorption reactions including adsorption, coprecipiation, and absorption.

Assessment on the Content of Heavy Metal in Orchard Soils in Middle Part of Korea (중부지역 과수원 토양중의 중금속 함량 평가)

  • Jung, Goo-Bok;Kim, Won-Il;Lee, Jong-Sik;Shin, Joung-Du;Kim, Jin-Ho;Yun, Sun-Gang
    • Korean Journal of Environmental Agriculture
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    • v.23 no.1
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    • pp.15-21
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    • 2004
  • Objectives of this study were to monitor the distribution of heavy metals, to compare extractable heavy metal with total content and to investigate the relationships between soil physico-chemical properties and heavy metals in orchard soil. Sampling sites were 48 in Gyeonggi, 36 in Gangwon, 36 in Chungbuk, and 44 in Chungnam, Soils were collected farm form two depths, 0 to 20 and 20 to 40 cm (here after referred to as upper and lower layers) from March to May in 1998. Total contents of heavy metal in soils were analyzed by ICP-OES after acid digestion ($HNO_3$:HCl:$H_2O_2$) whereas extractable contents were measured after successive extraction of 0.1N-HCl, 0.05 M-EDTA, and 0.005 M-DTPA. Mercury was analysed by mercury atomizer. The average contents of Cd Cu, and Pb in the extractant with 0.1N-HCl at upper layer were 0.080, 4.23, and 3.42 mg/kg, respectively. As content in the extractant with 1N-HCl was 0.44 mg/kg, and total contents of Zn, Ni and Hg were 78.9, 16.1, and 0.052 mg/kg, respectively. The ratios of concentrations of heavy metals to threshold values (Cd 1.5, Cu 50, Pb 100, Zn 300, Ni 40, Hg 4 mg/ke in Soil Environmental Conservation Act in Korea (2001) were low in the range of $1/2.5{\sim}1/76.9$ in orchard soils. The ratios of extractable heavy metal to total content ranged $5.4{\sim}9.21%$ for Cd, $27.9{\sim}47.8%$ for Cu, $12.6{\sim}21.8$% for Pb, $15.8{\sim}20.3%$ for Zn, $5.3{\sim}6.3%$ for Ni, and $0.7{\sim}3.6%$ for Zn, respectively. Cu and Pb contents in 0.05 M-EDTA extractable solution were higher than those in the other extractable solution. Total contents of Cd, Ni and Ni in soils were negatively correlated with sand content but positively correlated with silt and clay contents. Ratios of extractable heavy metal to total content were negatively correlated with clay content but ai and Ni contents were positively correlated with soil pH, organic matter, and available phosphorous. Therefore, the orchard soil was safe because the heavy metal contents of orchard soil were very low as compared to its threshold value in the Soil Environmental Conservation Act. However, it need to consider the input of agricultural materials to the agricultural land for farming practices for assessment of heavy metals.

Hydrochemistry and Occurrence of Natural Radioactive Materials within Borehole Groundwater in the Cheongwon Area (청원지역 시추공 지하수의 수리화학 및 자연방사성물질 산출 특성)

  • Jeong, Chan-Ho;Kim, Moon-Su;Lee, Young-Joon;Han, Jin-Seok;Jang, Hyo-Geun;Jo, Byung-Uk
    • The Journal of Engineering Geology
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    • v.21 no.2
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    • pp.163-178
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    • 2011
  • A test borehole was drilled in the Cheongwon area to investigate the relationship between geochemical environment and the natural occurrence of radioactive materials (uranium and Rn-222) in borehole groundwater. The borehole encountered mainly biotite schist and biotite granite, with minor porphyritic granite and basic dykes. Six groundwater samples were collected at different depths in the borehole using the double-packed system. The groundwater pH ranges from 5.66 to 8.34, and the chemical type of the groundwater is Ca-$HCO_3$. The contents of uranium and Rn-222 in the groundwater are 0.03-683 ppb and 1,290-7,600 pCi/L, respectively. The contents of uranium and thorium in the rocks within the borehole are 0.51-23.4 ppm and 0.89-62.6 ppm, respectively. Microscope observations of the rock core and analyses by electron probe microanalyzer (EPMA) show that most of the radioactive elements occur in the biotite schist, within accessory minerals such as monazite and limenite in biotite, and in feldspar and quartz. The high uranium content of groundwater at depths of -50 to -70 m is due to groundwater chemistry (weakly alkaline pH, an oxidizing environment, and high concentrations of bicarbonate). The origin of Rn-222 could be determined by analyzing noble gas isotopes (e.g., $^3He/^4He$ and $^4He/^{20}Ne$).

Neutralization of Acid Rock Drainage from the Dongrae Pyrophyllite Deposit: A Study on Behavior of Heavy Metals (동래 납석광산 산성 광석배수의 중화실험: 중금속의 거동 특성 규명)

  • 염승준;윤성택;김주환;박맹언
    • Journal of Soil and Groundwater Environment
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    • v.7 no.4
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    • pp.68-76
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    • 2002
  • In this study, we have investigated the geochemical behavior and fate of heavy metals in acid rock drainage (ARD). The ARD was collected from the area of the former Dongrae pyrophyllite mine. The Dongrae Creek waters were strongly acidic (pH : 2.3~4.2) and contained high concentrations of $SO_4$, Al, Fe, Mn, Pb, Cu, Zn, and Cd, due to the influence of ARD generated from weathering of pyrite-rich pyrophyllite ores. However, the water quality gradually improved as the water flows downstream. In view of the change of mole fractions of dissolved Fe, Al and Mn, the generated ARD was initially both Fe- and AA-ich but progressively evolved to more Al-rich toward the confluence with the uncontaminated Suyoung River. As the AR3 (pH 2.3) mixed with the uncontaminated waters (pH 6.5), the pH increased up to 4.2, which caused precipitation of $SO_4$-rich Fe hydroxysulfate as a red-colored, massive ferricrete precipitate throughout the Dongrae Creek. Accompanying the precipitation of ferricrete, the Dongrae Creek water progressively changed to more Al-rich toward downstream sites. At the mouth of the Dongrae Creek, it (pH 3.4) mixed with the Suyoung River (pH 6.9), where pH increased to 5.7, causing precipitation of Al hydroxysulfate (white precipitates). Neutralization of the ARD-contaminated waters in the laboratory caused the successive formation of Fe precipitates at pH<3.5 and Al precipitates at higher pH (4~6). Manganese compounds were precipitated at pH>6. The removal of trace metals was dependent on the precipitation of these compounds, which acted as sorbents. The pHs for 50% sorption ($pH_{50}$) in Fe-rich and Al-rich waters were respectively 3.2 and 4.5 for Pb, 4.5 and 5.8 for Cu, 5.2 and 7.4 for Cd, and 5.8 and 7.0 for Zn. This indicates that the trace metals were sorbed preferentially with increasing pH in the general order of Pb, Cu, Cd, and Zn and that the sorption of trace metals in Al-rich water occurred at higher pH than those in Fe-rich water. The results of this study demonstrated that the partitioning of trace metals in ARD is not only a function of pH, but also depends on the chemical composition of the water.

Monsoon Inflow as a Major Source of In-lake Phosphorus (호수내 인의 주요원으로 몬순 유입수)

  • An, Kwang-Guk
    • Korean Journal of Ecology and Environment
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    • v.33 no.3 s.91
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    • pp.222-229
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    • 2000
  • Spatial and temporal variation of phosphorus in response to intensity of summer monsoon was evaluated in Taechung Reservoir during 1993${\sim}$1994. Total phosphorus (TP) averaged 31 ${\mu}$g/l during the study and varied from 6 to 197 ${\mu}$g/l. Concentrations of TP were highest in the headwaters during the monsoon of July${\sim}$August 1993, and these values were mainly made of particulate P and were closely associated (R$^{2}$=0.74, p<0.001) with high inorganic suspended solids (NVSS). In-lake TP in the headwaters was mainly influenced by the watershed runoff and declined toward the dam. Values of TP downlake was only one-fifth of the peak in the headwaters and had no correlation with NVSS. In 1994, inlake TP was markedly lower relative to 1993 and showed low spatial and temporal variation. Maximum TP during monsoon 1994 in the headwaters and mid-lake was 72% and 52% lower, respectively, than in those two zones in 1993 whereas TP downlake was similar between the two years. These results suggest that temporal variation downlake is much less influenced by seasonal inflow compared to the haedwaters. In 1993, mean TP before fall overturn, based on average value for all sites, was significantly (t=5.99, p<0.001) greater than the mean after fall overturn, whereas in 1994 mean TP after fall overturn (32 ${\mu}$g/l) was greater. This outcome indicates that in 1993 major P-input originated from the external source from the watershed during the intense monsoon, whereas in 1994 internal processes dominated during the weak monsoon. Overall data suggest that annual budget of inlake P is regulated by intensity of the summer monsoon, and phosphorus data measured at single site near the dam or headwater zone may not be represent seasonal trends of the system due to large spatial variation of Taechung Reservoir.

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Characteristics of Fish Community in Gap Stream by Habitat Type (서식처 유형에 따른 갑천의 어류군집 특성)

  • Lee, Dong-Jun;Byeon, Hwa-Kun;Choi, Jun-Kill
    • Korean Journal of Ecology and Environment
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    • v.42 no.3
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    • pp.340-349
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    • 2009
  • The natural type section of Gap Stream was divided into 7 sites, such as, closed pool, runs, riffle, opened pool, pool, reek-scattered riffle, and Dam-type pool. The ecological characteristics of fish community at each site was examined from April, 2007 to October, 2008. During the survey period, 29 species belonging to 8 families were collected, and Carassius auratus (St. 1), Coreoleuciscus splendidus (St. 3), Acheilognathus lanceolatus (St. 4) and Zacco platypus (St. 2, 5, 6, 7) were characteristic species that represent each habitat. The species of C. auratus preferred physical habitat with sand-bottom pool, moderate depth of 65$\sim$90 cm, and stagnant water. The species of C. splendidus mainly preferred physical habitat with cobbles and pebbles are scattered riffles (St. 3), moderate depth of 65$\sim$90 cm, and flow velocity is 0.14$\sim$0.85 m $sec^{-1}$. It also preferred where concentration of BOD, COD, TN, TP and SS is low and DO's value is high, because the flow velocity is fast. A. lanceolatus preferred where the depth of water is low (3$\sim$44 cm) like an opened pool (St. 4) and the flow velocity is slow (0.01$\sim$0.02 m $sec^{-1}$). Z. platypus dominated in a variety of habitats such as runs (St. 2), pool (St. 5), rock-scattered riffles (St. 6) and D-type pool (St. 7), and it preferred places where flow is abundant and riverbed structure is diverse. On the other hand, 4 individuals of Iksookimia choii appeared at reek-scattered riffles (St. 6). I. choii appeared in this research lived in where the width of river is 24 m, the depth of water is 3$\sim$35 cm and the flow velocity is 0.01$\sim$0.49 m $sec^{-1}$, and riverbed structure was diversely formed with boulder to sand. Also, water temperature, EC, BOD, COD, TN and TP was low, but concentrations of DO and SS were high comparatively. Therefore, it seems that I. choii can live only in physical and chemical environment with similar conditions.

Surface Texture Changes due to the Oxidation of Pyrite by Acidithiobacillus Ferrooxidans (애시디싸이오바실러스 페로악시댄스에 의한 황철석 산화에 따른 표면 조직의 변화)

  • Yu, Jae-Young;Koh, Hyun-Jin;Song, Hong-Gyu
    • Journal of the Mineralogical Society of Korea
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    • v.24 no.3
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    • pp.235-244
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    • 2011
  • A batch experiment of pyrite oxidation was performed and the surfaces of the reacted pyrite were regularly observed with the scanning electron microscope (SEM) together with the chemical compositions of the solution to help understand the oxidation mechanisms of pyrite by Acidithiobacillus ferrooxidans (Af). The dissolved Fe concentrations clearly indicated that Af experiences the lag and then exponential growth phase. An Af cell was observed to be attached to the surface of pyrite during the lag, implying that a direct leaching by the microbe really happens for the period. It is not certain, however, whether the main mechanism of pyrite oxidation during that time was the direct leaching or not, because there were just a few cells confirmed to be attached and most of the dissolved Fe was Fe(III). The dissolved Fe concentration stayed almost constant from the mid-lag phase to just before the onset of the exponential phase, suggesting that AI needs an adaptation time to switch its oxidation mechanism from one to the other whichever it is during that stage of growth. The moment of Af's cell division was observed by SEM on the surface of pyrite during the lag phase. The corrosion outline around the dividing cell was quite similar to the shape of the cell itself, which implies that the rate of the microbial oxidation is very uneven and the rate when the cell metabolizes should be much faster than that calculated from the concentration variation of the dissolved Fe. The number of etch holes by Af is much higher on the inoculated surfaces, indicating the average rate of pyrite oxidation is also much faster than that of abiotic oxidation. The microbial etch holes on pyrite surface are small and deep, which may influence the transition of the growth phases of Af from lag to exponential.

Chemical Characteristics for Hydrothermal Alteration of Surface Sediments from Submarine Volcanoes of the Tonga Arc (통가열도 해저화산 표층 퇴적물 내 열수변질의 화학적 특성)

  • Um, In Kwon;Chun, Jong-Hwa;Choi, Hunsoo;Choi, Man Sik
    • Journal of the Mineralogical Society of Korea
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    • v.26 no.4
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    • pp.245-262
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    • 2013
  • We analyzed 29 surface sediment samples in five submarine volcanoes (TA12, TA19, TA22, TA25, and TA26) located in the southern part of the Tonga arc for trace elements and rare earth elements to investigate characteristics of the hydrothermal alteration of surface sediments. Based on analytical results of trace element and rare earth element (REE), surface sediments of TA12, TA19, and TA22 submarine volcanoes, which are located in the northern part of the study area, were very little or not influenced by hydrothermal fluids. In contrast, some stations of TA25 and TA26 submarine volcanoes were strongly affected by hydrothermal fluids. However, these two submarine volcanoes showed different features in element concentration in the sediments. Some stations of TA25 submarine volcano showed enrichment of Ni, Cu, Sn, Zn, Pb, Cr, Cd, Sb, W, Ba, Ta, Rb, Sr, and As, however, those of TA26 submarine volcano showed enrichment of Sn, Zn, Pb, Cd, Sb, Ba, Rb, and Sr. Stations which enriched trace elements were observed, enriched REEs were also observed. Average upper continental crust (UCC)-normalized REE patterns of the surface sediments generally showed low light REE (LREE) abundances and increased heavy REE (HREE) abundances. Eu enrichment was identified at several stations of TA25 and TA26 submarine volcanoes. In addition, enrichment of Ce was found at some stations of TA26 submarine volcano and these enrichment patterns were similar with hydrothermal fluid of near stations. Furthermore, TA25 and TA26 submarine volcanoes showed different enrichment characteristics of trace elements and REE. Trace elements were concentrated at TA25 submarine volcano. TA26 submarine volcano, on the other hand, observed highly enrichment of REE especially, Eu and Ce. As a result of the investigation, the characteristics and concentrations of REEs and trace elements in the surface sediments of each submarine volcano can be applied to identify hydrothermal alteration of sediments during exploration for hydrothermal deposits.

Regional Analysis of Forest Eire Occurrence Factors in Kangwon Province (강원도 지역 산불발생인자의 지역별 유형화)

  • 이시영;한상열;안상현;오정수;조명희;김명수
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.3 no.3
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    • pp.135-142
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    • 2001
  • This study attempts to categorizes the factors of forest fire occurrences based on regional meteorologic data and general forest no characteristics of 18 cities and guns in Kangwon province. lo accomplish this goal, some statistical analyses such as analysis of variance, correspondence analysis and multidimensional scaling were adopted. To reveal the forest fires pattern of study region, a categorization process was conducted by employing the quantification approach which modified and quantified the metric-data of fire occurrence dates. Also, The fire occurrence similarity was compared by using multidimensional scaling for each study region. The major results are summarized as follows: It was found that the meteorological factors emerged as different to each region are average and maximum temperature, minimum dew point temperature and average and maximum wind speed. In the result of correspondence analysis representing relationships between fire causes and study regions, Kangrung is caused by arsonist, Chulwon, Hwachen and Yanggu caused by military factor, Sokcho and Chunchen caused by the debris burning, and Samchuk caused by general man-caused fires, respectively. Finally, the forest fire occurrence pattern of this study regions were divided into five areas such as, group I including Samchuk, Kangryung, Chunchen, Wonju, Hongchen and Hhoingsung, group II including Donghae, Taebaek, Yangyang and Pyongchang, group III including Jungsun, Chulwon and Whachen, group Ⅵ including Gosung, Injae and Yanggu, and group V including Shokcho and Youngwol.

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