• Economic and Environmental Geology
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• v.42 no.5
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• pp.479-486
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• 2009

In natural environments, manganese (Mn) exists in the valence of +2, +3, and +4 and plays a pivotal role as a strong oxidant or reductant in the geochemical cycles of elements. Especially, Mn forms varying (oxyhydr)oxides. The oxidation state of structural Mn is characteristic to each oxide and is one of the most important factors controlling its geochemical behaviors such as solubility, sorption capacity, and redox potential. Therefore, it is important to elucidate processes governing Mn oxidation state in predicting the fate and transport of many redox sensitive elements in the environment. X-ray photoelectron spectroscopy (XPS) is a very useful method to determine the oxidation state of various elements in solid phases. In this study, the oxidation states of structural Mn in MnO, $Mn_2O_3$, $MnO_2$ were assessed based on the binding energy spectra of $Mn2p_{3/2}$ and Mn3s using XPS and were compared with those reported elsewhere. $Mn2p_{3/2}$ binding energies were determined as 640.9, 641.5, 641.8 eV for MnO, $Mn_2O_3$, $MnO_2$, respectively, which indicates that the binding energy increased with increasing Mn oxidation state. It was also noted that Ar etching may cause changes in electronic structure configuration on surface of the original sample.

• Proceedings of the Mineralogical Society of Korea Conference
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• 2001.06a
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• pp.115-115
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• 2001

경주시 양남면의 4기 단층으로 추정되는 수렴단층에 의해 절단되는 해안단구 퇴적층 풍화단면에서 저결정질 광물인 앨로패인 교결층을 기재하였다. 이들은 자갈퇴적층 내에 협재하는 수조의 모래층에 한정되어 형성되어 있으며, 3-17 cm 두께로 연장성이 매우 좋다. 편광현미경 관찰에 의하면 모래층에는 사장석편들이 다량 함유되어 있으며 앨로패인은 광학적 등방성의 치밀한 점토집합체들로서 사장석 입자를 선택적으로 교대하거나 자갈과 모래입자들을 피복하고 있다. 앨로패인은 광학적 이방성인 상하위층의 고령토질 점토피복물과 명확히 구분된다. 앨로패인의 전자현미분석에 의하면, Al/Si 원자비가 1.3-1.7 범위이고 평균값은 1.5이다. X선회절분석 결과 3.49$\AA$과 2.26$\AA$에서 두 개의 넓은 회절대가 관찰된다. 주사 및 투과전자현미경관찰에 의하면 앨로패인을 특정한 입자형태 없이 치밀한 겔상태를 이루고 있다. 열분석에 의하면 96$^{\circ}C$에서 큰 흡열피크와 992$^{\circ}C$에서 발열피크가 관찰되며, 총 45% 정도의 중량감소를 보인다. 사장석의 평균조성은 An$_{87}$이며, 사장석내 유리포유물의 전자현미분석결과는 화산암 화학분류도에서 현무암 영역에 도시된다. 이 지역의 기반암은 현무암질 라필리응회암이나 사장석편을 제외하고 벤토나이트화되어 있다. 따라서 해빈환경에서 사장석이 벤토나이트에서 분리되어 퇴적한 것으로 보인다. 앨로패인 교결층은 해수면 강하로 단구퇴적층이 지표로 노출된 후, Al의 함량이 높고 비교적 풍화에 약한 사장석이 선택적으로 풍화되어 생성되었다. 앨로패인으로 피복된 모래층 내의 자갈은 풍화반응이 지체되어 상하위층의 자갈과 비교하여 풍화도에 있어서 현저한 차이를 보인다.. 파이프 중심에서 외곽부로 갈수록 전기석의 함량은 줄어들고 있고 장석들이 알바이트ㆍ칼스베드 쌍정을 보이며, 흑운모가 각섬석보다는 우세하게 나타나고 있다. 전기석은 주상 결정, 자형 내지 반자형의 입자로 다색성을 보이며, 결정 중심에서 가장자리로 갈수록 파란색과 황갈색의 광학적 누대구조를 관찰할 수 있다. 일광광산에서 산출되는 전기석에 대한 현미경 관찰은 열수기원임을 지시하고 있다. 야외조사와 현미경 관찰의 예비조사에 의하면 일광광산의 전기석이 형성된 환경은 다른2가지 화학적인 저장소의 혼합 효과의 결과로 생성되어진 것으로 예상된다. 일광의 화강암류를 만든 마그마는 전기석을 형성할 만큼의 Fe-Mg성분이 충분하지 않았을 것이다. 화강암 내에 흑운모와 각섬석의 결정작용에 의해 마그마의 Fe-Mg성분이 고갈되어지고 이로 인해 그 함량이 감소하며 상대적으로 마그마 내에 남은 붕소(B$_2$O$_3$)는 열수로 용리되고 흑운모, 각섬석과 평형을 유지하며 열수에 남아있게 된다. 잔류용융체에 남은 붕소의 함량은 전기석을 만들기에 충분함에도 불구하고, Fe-Mg 함량이 부족하여 마그마 기원의 전기석 결정을 만들 수가 없다가 광맥이 형성된 시기에 또 다른 열수가 공급되면서 이전의 평형이 깨지고 기존의 흑운모와 같은 염기성 광물이 붕소(B)를 함유한 새로운 열수와 반응하여 전기석을 형성한 것으로 예상한다. 앞으로 전암과 광물에 대해 지화학적 연구를 통해 화강암류와 전기석과의 지화학적 연관성, 주성분 원소와 열수의 특성과의 상관관계, 전기석의 기원(마그마 기원인지 열수기원인지)이 보다 정확하게 파악될 것이다. 마그마 진화에 따른 전기석의 성분변화와 기원을 이용하여 일광광산의 동광화대를 형성한 마그마 계에서 열수계로 이어지는 지질학적 과정을 이해할 수 있을 것이며, 암석 성인론적 지시자로서

• Journal of the Korean earth science society
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• v.28 no.1
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• pp.112-122
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• 2007

It is known that coal-derived fly ashes have the unique chemical composition and mineralogical characteristics. Since iron oxides in coal fly ash are enriched with heavy metals, the subsurface media including soils, underground water, and sea water are highly likely contaminated with heavy metals when the heavy metals are leached from fly ashes by water-fly ash interactions. The purpose of this study was to investigate how indigenous bacteria affect heavy metal leaching and mineralogy in fly ash slurry during the fly ash-seawater interactions in the ash pond located in Dangjin seashore, Korea. The average pH of ash pond seawater was 8.97 in nature. Geochemical data showed that microbial activity sharply increased after the 7th day of the 60-day course batch experiments. Compared with other samples including autoclaved and natural samples, ${SO_4}^{2-}$ was likely to decrease considerably in the fly ash slurry samples when glucose was added to stimulate the microbial activity. Geochemical data including Eh/pH, alkalinity, and major and trace elements showed that the bacteria not only immobilize metals from the ash pond by facilitating the chemical reaction with Mn, Fe, and Zn but may also be able to play an important role in sequestration of carbon dioxide by carbonate mineral precipitation.

• Economic and Environmental Geology
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• v.45 no.2
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• pp.105-119
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• 2012

Indigenous bacteria isolated from contaminated sites play important roles to remediate contaminated groundwater. Chromium has the most stable oxidation states. Cr(VI) is toxic, carcinogenic, and mobile, but Cr(III) is less toxic and immobile. In this study, indigenous microorganism (MMPH-0) was enriched from Cr(VI) contaminated groundwater, and identified by 16S rRNA gene analysis. Using MMPH-0, the effect of stimulating with e-donors (glucose, lactate, acetate, and no e-donor control), respiration conditions, biomass, tolerance, and geochemical changes on Cr(VI) reduction were investigated in batch experiments for 4 weeks. The changes of Cr(VI) concentration and geochemical conditions were monitored using UV-vis-spectrophotometer and Eh-pH meter. And the morphological and chemical characteristics of MMPH-0 and precipitates in the effluents were characterized by TEM-EDS and SEM-EDS analyses. MMPH-0 (Enterobacter aerogenes) was able to tolerate up to 2000 mg/L Cr(VI) and reduce Cr(VI) under aerobic and anaerobic conditions. MMPH-0 performed faster and higher efficiency of Cr(VI) reduction with electron donors (over 70% after 1 week with e-donor, 10-20% after 4 weeks without e-donor). The changes of Eh-pH in effluents showing the tendency from oxidizing to reducing condition and a bit of acidic change in pH due to microbial oxidation of organic matters donating electrons and protons suggested the roles of MMPH-0 on Cr(VI) in the contaminated water catalyzing to transit geochemical stable zone for more stable $Cr(OH)_3$ or Cr(III) precipitates. TEM/SEM-EDS analyses of MMPH-0 and precipitates indicate direct and indirect Cr(VI) reduction: extracellular polymers capturing Cr component outside cells. These results suggested diverse indigenous bacteria and their biogeochemical reactions might enhance more effective and feasible remediation technology of redox sensitive heavy metals in metal-contaminated in groundwater.

• Economic and Environmental Geology
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• v.28 no.4
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• pp.351-367
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• 1995

The elemental geochemistry and oxygen isotopes of illite/smectite (I/S) have been studied in relationship to the mineralogical trend in the Reindeer D-27 well, Beaufort-Mackenzie Basin. The increase in concentrations of $K_2O$, Rb and rare earth elements (REE), the decrease in concentrations of tetrahedral elements such as Mg, Ti, Sc, Zn and Zr, and the increase in concentrations of tetrahedral elements such as Be and V can be related to I/S compositions that vary systematically with depth. Layer formulae of S- and I-layers are estimated as $[Al_{1.57}Fe_{.19}Mg_{.31}Ti_{.07}][Si_{3.84}Al_{.16}]O_{10}(OH)_2$ and $[Al_{1.84}Mg_{.16}][Si_{3.33}Al_{.67}]O_{10}(OH)_2$, respectively. The mobilization of REE appears to occur during illitization. The increase in concentrations of REE, especially La and Ce, with depth is probably linked to incorporation of ions with high valency (e.g. $V^{5+}$) in tetrahedral sites. The excess valency due to V is partly counter-balanced by ions with low valency (e.g. $Be^{2+}$) and, in turn, the local valency deficiency caused by $Be^{2+}$ could be compensated by high-charge interlayer cations such as REE (＋3). ${\delta}^{18}O$ values of I/S range from 2.91 to 15.72‰ (SMOW), and increase with depth, contrasting to trends observed in the Gulf Coast and elsewhere. The increase in ${\delta}^{18}O$ of I/S results from the rapid increase in ${\delta}^{18}O$ of pore water that overcomes the decrease in temperature-dependent fractionation values with increasing burial depth (${\delta}^{18}O_{pore\;water}>-d{\Delta}/_{I/S-water};\;d{\delta}^{18}O_{I/S}>0$). Calculated ${\delta}^{18}O$ values of pore water in equilibrium with I/S suggest that the original water was probably meteoric water. The stratification of pore water is postulated from the presence of an isotopically light interval, about 450m thick. The depth range of the isotopically light zone overlaps, but does not coincide with the interval of lowered I-content and $K_2O$ concentrations, suggesting that oxygens may have been exchanged independently of mineralogical and geochemical reactions.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.729-744
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• 2023

The value of lithium has significantly increased due to the rising demand for electric cars and batteries. Lithium is primarily found in pegmatites, hydrothermally altered tuffaceous clays, and continental brines. Globally, groundwater-fed salt lakes and oil field brines are attracting attention as major sources of lithium in continental brines, accounting for about 70% of global lithium production. Recently, deep groundwater, especially geothermal water, is also studied for a potential source of lithium. Lithium concentrations in deep groundwater can increase through substantial water-rock reaction and mixing with brines. For the exploration of lithim in deep groundwater, it is important to understand its origin and behavior. Therefore, based on a nationwide preliminary study on the hydrogeochemical characteristics and evolution of thermal groundwater in South Korea, this study aims to investigate the distribution of lithium in the deep groundwater environment and understand the geochemical factors that affect its concentration. A total of 555 thermal groundwater samples were classified into five hydrochemical types showing distinct hydrogeochemical evolution. To investigate the enrichment mechanism, samples (n = 56) with lithium concentrations exceeding the 90th percentile (0.94 mg/L) were studied in detail. Lithium concentrations varied depending upon the type, with Na(Ca)-Cl type being the highest, followed by Ca(Na)-SO₄ type and low-pH Ca(Na)-HCO₃ type. In the Ca(Na)-Cl type, lithium enrichment is due to reverse cation exchange due to seawater intrusion. The enrichment of dissolved lithium in the Ca(Na)-SO₄ type groundwater occurring in Cretaceous volcanic sedimentary basins is related to the occurrence of hydrothermally altered clay minerals and volcanic activities, while enriched lithium in the low-pH Ca(Na)-HCO₃ type groundwater is due to enhanced weathering of basement rocks by ascending deep CO₂. This reconnaissance geochemical study provides valuable insights into hydrogeochemical evolution and economic lithium exploration in deep geologic environments.

• Journal of the Mineralogical Society of Korea
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• v.13 no.2
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• pp.73-83
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• 2000

다덕 광산 폐석내 섬아연석과 함망간탄산염 광물의 풍화현상과 그에 따른 중금속의 거동을 조사 하였다. 섬아연석은 풍화초기에 극미립 산화철의 망상구조 집합체로 교대되었으며, 후기에는 자연황이 용해중인 섬아연석과 산화철 집합체 사이에 침전되었다. 산화철 집합체에는 As가 다량 함유되어 있다. 능망간석와 함망간 방해석은 함아연산화망간의 망상구조 집합체로 교대되었으며, 함망간방해서과 함아연산화망간 사이에는 스미소나이트가 침전되었다. 선택적 용해외 X선회절분석을 이용하여 감정한 결과, 함아연산화망간은 헤테롤라이트/하이드로헤테롤라이트인 것으로 판명되었다. Zn의 일부는 규산과 결합하여 입간 공극에 월레마이트로 침전되었다. 풍화 초기에 형성되는 극미립 산화철 및 함아연산화망간의 치밀한 망상 집합체는 풍화용액의 순환을 차단하여, 모광물의 풍화 반응을 지체시키는 지화학적 장벽 역할을 하였다. 이에 따라 망상구조 내에 조성된 국지적 미환경하에서 풍화중간산물들이 침전되었다. 이상의 연구 결과로 다음과 같은 사항을 추론할 수 있다. 섬아연석의 Fe와 함망간탄산염의 Mn은 각각 산화철과 산화망간으로 침전되어 산성화에 기여하였다. 폐광석 더미내 As의 활동도는 저결정질 산화철에의 흡착에 의해 조절되며, Zn의 활동도는 미소환경조건에 따라 하이드로헤테롤라이트/헤테롤라이트, 스미소나이트, 월레마이트 등의 다양한 이차광물의 용해도에 의하여 조절된다.

• The Korean Journal of Quaternary Research
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• v.10 no.1
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• pp.27-52
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• 1996

금강 퇴적물의 지화학적 특성을 파악하기 위하여 상류에서 하류까지 21개의 표층 퇴적물을 채취하고 총금속(Al, Fe, Mn, Cr, Co, Ni, Cu, Zn, Pb) 입도별 금속 및 존재형태별 금속을 분석하였다. 또한 하천에서 연안역까지 미량금속의 공간적 변화를 보기 위해 부유물 을 일정 간격으로 채취하여 미량금속을 분석하였다. 퇴적물 중 미량 금속 함량을 평균 입도 와 밀접히 관계하여 변화하며 세립질실트 이하 부분에서 가장높은 함량을 보였고 이 높은 함량은 하천 부유물 중 금속 함량과 Mn을 제외하고 거의 유사한 수준이었다. Pb은 조립질 모래에서도 높은 함량을 보이는데 이는 조립질 모래에 많이 포함된 정장석에 의한 영향이 되고 세립질 실트에서의 높은 금속 함량은 세립한 중광물에 의한 영향이다. Mn과 Pb을 제 안한 금속들은 퇴적물 중 주로(70% 이상) 결정 격자와 관계하여 존재하는데 이는 퇴적물의 주구성 입도가 조립하여 금속이 풍부하고 세립한 중광 물에 의한 영향이 크기 때문이다. 하 천에서 염하구로 금속 함량이 급격히 감소하는데 이는 용존 $Mn^{+2}$이온이 $MnO_2$로 변화하는 산화반응과 하천구역에서의 퇴적 그리고 염하구에서 금속이 적어 진 입자(염하구 내에서 유기물 분해/용해로 만들어지거나 재부유 작요에 의한 조립질 물질) 와 하천 부유물과의 혼합작용에 의해 이루어진다.

• Economic and Environmental Geology
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• v.32 no.1
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• pp.101-111
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• 1999

Sedimentary organic matter, exposed to continental surficial environment, reacts with oxygen supplied from the atmosphee and forms carbon-containing oxidation products. Knowledge of the rate and mechanisms of sedimentary organic matter weathering is important because it is one of the major controls on atmospheric oxygen level through geologic time. Under the abiological conditions, the oxidation rate of coal organic matter by molecular oxygen is enhanced by the increase of oxygen concentration and temperature. At ambient temperature and pressure, aqueous coal oxidation results in the formation of dissolved $CO_2$ dissolved organic carbon and solid oxidation products which are all quantitatively significant reaction products. The effects of pH, ultraviolet light, and microbial activity on the weathering of sedimentary organic matter are poorly contrained. Based on the results of geochmical and environmental studies, it is believed that the photochemical reaction should play an important role in the decomposition and oxidation of sedimentary organic matter removed from the weathering profile. At higher pH conditions, the production rate of DOC can be accelerated due to base catalysis. These high molecular weight oranic matter can react with man-made pollutants such as heavy metal ions via adsorption/desorption or ion exchange reactions. The effect of microbial activity on the oxidative weathering of sedimentary organic matter is poorly understood and remains to be studied.

• Journal of the Mineralogical Society of Korea
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• v.10 no.1
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• pp.33-44
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• 1997

The reaction path of water-gneiss in 200m borehole at the Soorichi site of Yugu Myeon, Chungnam was simulated by the EQ3NR/EQ6 program. Mineral composition of borehole core and fracture-filling minerals, and chemical composition of groundwater was published by authors. In this study, chemical evolution of groundwater and formation of secondary minerals in water-gneiss system was modelled on the basis of published results. The surface water was used as a starting solution for reaction. Input parameters for modelling such as mineral assemblage and their volume percent, chemical composition of mineral phases, water/rock ratio reactive surface area, dissolution rates of mineral phases were determined by experimental measurement and model fit. EQ6 modelling of the reaction path in water-gneiss system has been carried out by a flow-centered flow through open system which can be considered as a suitable option for fracture flow of groundwater. The modelling results show that reaction time of 133 years is required to reach equilibrium state in water-gneiss system, and evolution of present groundwater will continue to pH 9.45 and higher na ion concentration. The secondary minerals formed from equeous phase are kaolinite, smectite, saponite, muscovite, mesolite, celadonite, microcline and calcite with uincreasing time. Modeling results are comparatively well fitted to pH and chemical composition of borehole groudwater, secondary minerals identified and tritium age of groundwater. The EQ6 modelling results are dependent on reliability of input parameters: water-rock ratio, effective reaction surface area and dissolution rates of mineral phases, which are difficult parameters to be measured.