• Economic and Environmental Geology
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• v.50 no.6
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• pp.545-554
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• 2017

Birnessite is one of the dominant Mn (oxyhydr)oxide phases commonly found in soil and deep ocean environments. It typically occurs as nano-sized and poorly crystalline aggregates in the natural environment. It is well known that birnessite participates in a wide variety of bio/geochemical reactions as a reactive mineral phase with structural defects, cation vacancies, and mixed valences of structural Mn. These various bio/geochemical reactions control not only the fate and transport of inorganic and organic substances in the environment, but also the formation of diverse Mn (oxyhydr)oxides through birnessite transformation. This review assessed and discussed about the phase transformation of birnessite under a wide range of environmental conditions and about the potential geochemical factors controlling the corresponding reactions in the literature. Birnessite transformation to other types of Mn (oxyhydr)oxides were affected by dissolved Mn(II), dissolved oxygen, solution pH, and co-existing cation (i.e., $Mg^{2+}$). However, there still have been many issues to be unraveled on the complex bio/geochemical processes involved in the phase transformation of birnessite. Future work on the detail mechanisms of birnessite transformation should be further investigated.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.32 no.5
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• pp.680-687
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• 1999

To understand the role of shelf sediment in phosphorus biogeochemical cycle, we carried out sequential sediment extraction (SEDEX) of P and porewater analysis on 14 core samples collected in the South Sea of Korea, SEDEX classified P-pools into 5 phases and results are grouped into two categories: reactive P (loosely sorbed-P and Fe bound-P) and refractory P (detrital inorganic-p, authigenic mineral-P and organic-P). Total P concentrations are decreased with sediment depth in all samples as a result of dissolution to porewater. Reactive P comprises about $20\~50\%$ of total P, and iron bound-P is the major form consisting $70\~80\%$ of reactive P-pool. Iron bound-P decreases sharply with depth. Depth profiles of dissolved P concentration in porewater show mirror image of iron bound-P, revealing the role of FeOOH as a regulator of reactive P supply to overlying water column. Authigenic mineral-P consists less than $5\%$ of total P, thus removal of reactive P by converting into refractory P seems inefficient in shelf sediment. This implies that continental shelf sediment sequesters P temporarily rather than permanently. Results show local variation. Nakdong estuary receiving large amount of terrigenous input shows the highest concentration of total P and reactive P. Here iron oxyhydroxides at the surface sediment control the water column flux of P from sediment. Although total P content at the surface is comparable (500$\~$600 ${\mu}g{\cdot}g^{-1}$) between the South Sea and East China Sea, the former contains more iron bound-P and less derital inorganic-P than the latter. Reasons for the difference seem due in part to particle texture, and to biological productivity which depends roughly on the distance from land.

• 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.42 no.6
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• pp.527-539
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• 2009

The Kumho River flows through volcanic and sedimentary rocks at upstream and downstream regions and also through industrial district including dyeing complex before it meets the Nakdong River, and as a result, many factors can influence the geochemistry of river water. The concentrations of dissolved ions generally increased as it flows downstream. The concentrations of cations are in the order of Ca>Na>Mg>K, and those of anions are $HCO_3$>$SO_4$>Cl>$NO_3$. These results show that the weathering of sandstone and shale containing carbonate including calcite caused the enrichment of Ca and $HCO_3$. At first 4 sampling sites, Si contents are relatively high mainly due to the weathering of silicate minerals of volcanic rocks. However, Na and $SO_4$ contents are higher at downstream sites due to the industrial and municipal sewage. Piper diagram also shows that the geochemical patterns changed from Ca-$HCO_3$ to Ca-Cl/Ca-$SO_4$ and Na-Cl/Na-$SO_4$ type. When comparing the samples collected in May and July, the concentrations of dissolved ions in July are generally lower than those in May, which indicates that dilution by precipitation played an important role. In July the relative concentration of Ca increased, indicating that Ca in soils probably from fertilizer were mixed into the river water by precipitation. The river waters are mainly from precipitation. The dissolved ions are mainly from weathering of carbonate minerals and pollutants from municipal sewage and discharged water from industrial complex. The composition of oxygen and deutrium isotope in July showed higher values, which is contrary to the amount effect, maybe due to Youngchon Dam. The nitrogen isotope showed lower values in July than those in May, which can be interpreted to indicate mixing of nitrate from soils and fertilizer in the cultivated land by the heavy rain. The isotope composition of nitrate increased downstream, indicating that the influence of sewage and animal manure also increased downstream.

• 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.

• Economic and Environmental Geology
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• v.47 no.1
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• pp.61-69
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• 2014

As we are trying to in-situ treat (purify or immobilize) heavy metals or radionuclides in groundwater, one of the geochemical factors to be necessarily considered is the value of oxidation/reduction potential (ORP) of the groundwater. A biogeochemical impact on the characteristic ORP change of groundwater taken from the KAERI underground was observed as a function of time by adding electron-donor (lactate), electron-acceptor (sulfate), and indigenous bacteria in a laboratory condition. There was a slight increase of Eh (slow oxidation) of the pure groundwater with time under a $N_2$-filled glove-box. However, most of groundwaters that contained lactate, sulfate or bacteria showed Eh decrease (reduction) characteristics. In particular, when 'Baculatum', a local indigenous sulfate-reducing bacterium, was injected into the KAERI groundwater, it turned to become a highly-reduced one having a decreased Eh to around -500 mV. Although the sulfate-reducing bacterium thus has much greater ability to reduce groundwater than other metal-reducing bacteria, it surely necessitated some dissolved ferrous-sulfate and finally generated sulfide minerals (e.g., mackinawite), which made a prediction for subsequent reactions difficult. As a result, the ORP of groundwater was largely affected even by a slight injection of nutrient without bacteria, indicating that oxidation state, solubility and sorption characteristics of dissolved contaminants, which are affected by the ORP, could be changed and controlled through in-situ biostimulation method.

• Economic and Environmental Geology
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• v.49 no.3
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• pp.167-179
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• 2016

Water quality of Oseepchun, Dogye area, was investigated quantitatively for its origin and hydrogeochemistry in relation to the influence of groundwater. Groundwater appears to be the principal source of Oseepchun from the water-quality monitoring data including redox potentials, composition of dissolved ions and their correlations, hydrogen and oxygen stable isotopic ratios, and the distribution and occurrence of contaminants. Water-quality type of the surface water was grouped by the water-rock interactions as $Ca-HCO_3$ type originated from carbonated bed-rocks in the Joseon Supergroup, (Ca, Mg)-$SO_4$ type related with dissolution of surfide minerals in coal beds of Pyeongan Supergroup, and (Ca, Mg)-($HCO_3$, $SO_4$) type of the mixed one. Locally water pollution occurs by high $SO_4$ from mine drainage and $NO_3$ from waste-treatment facility. Intensive precipitation in summer has no effect on the water type of Oseepchun, but increases the inflow of nitrate and chloride originated from land surface. Results of this study direct that groundwater-surface water interaction is intimate, and thus surface-water resource management should begin with groundwater characterization.

• The Journal of Engineering Geology
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• v.13 no.1
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• pp.1-16
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• 2003

Geochemical characteristics of groundwater in the different kinds of various lithology such as Haman formation, Panyaweol formation, Jusan andesitic formation and Palgongsan granite is distinguished by mineralogical and chemical compositions. The Concentration of the majority of solutes in groundwaters of Haman and Panyaweol formation is higher than in that of andesite and granite. Higher concentration of $HCO_3^{-}{\;}and{\;}SO_4^{2-}$ anions in the groundwater is peculiar. High concentrations of $Ca^{2+},{\;}Mg^{2+},{\;}HCO_3^{-}$ in the groundwaters of the sedimentary rocks result mainly from reaction of $CO^{2-}$ charged water with calcite and weathered feldspars. With the Piper diagram, the groundwaters of Haman formations are mainly plotted in $CaSO_4-CaCl_2$ type, whereas those of Panyaweol formations are plotted in the bothside of $Ca(HCO_3)_2{\;}and{\;}CaSO_4-CaCl_2$ type. Thses two different types of $Ca(HCO_3)_2{\;}and{\;}CaSO_4-CaCl_2$ groundwater were originated from dissolution of calcite($Ca(HCO_3)_2)$ and the oxidation of pyrite($CaSO_4-CaCl_2$), respectively. And it also is influenced by anthropogenic contamination. Three factors were extracted from the factor analysis for chemical data. Factor 1, controlled by $SO_4^{2-},{\;}Na^{+},{\;}Ca^{2+}$ and Fe, explains the dissolution of calcite, plagioclase and oxidation of pyrite. Factor 2, controlled by $HCO_3^{-}{\;}and{\;}Mg^{2+}$, mainly explains the dissolution of Mg-carbonates and dolomitization. Factor 3, controlled by $Cl^{-},{\;}K^{+}{\;}and{\;}NO_3^{-}$, is subject to the influence of artificial pollution including industrial waste water disposal. In this study area, some industrial complex which is close to Keumho river show the higher score of factor 3.

• Korean Journal of Ecology and Environment
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• v.44 no.4
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• pp.347-357
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• 2011

We examined two reservoirs (Inkyung res. and Joongang res.) and two streams (Kyungan str. and Jecheon str.), all of which were eutrophic, during the 2010 warm season, to evaluate the water quality improvement activity (WQIA) of plant-mineral composite (PMC), which was previously developed to control suspended solids, including cyanobacterial bloom (Kim et al., 2010). We simultaneously measured both solid (S-MCLR) and dissolved microcystin-LR (D-MCLR), before and after PMC treatment, in the Joongang reservoir. Taking water body size and volume into account, we conducted the whole-scale experiment in the Inkyung reservoir, and mesocosm-scale experiments in the other three systems. The WQIAs of PMC were found to be comparatively high in SS (70~81%), TP (75~91%), BOD (65~91%), Chl-a (88~98%), phytoplankton (84~92%) and zooplankton (68~88%), except for the Kyungan stream, which was below 45% in all parameters. After PMC treatment, the concentrations of both SMCLR (47%) and D-MCLR (96%) decreased within two days, suggesting a mitigation possibility of hazardous chemicals such as agrochemicals and endocrine disrupters in the aquatic ecosystem. Our results collectively indicate that PMC is a useful agent to control suspended solids, including nuisance cyanobacterial bloom and their exudates, in an undisturbed water system with a long residence time.

• The Journal of Engineering Geology
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• v.33 no.3
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• pp.413-426
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• 2023

This study presents the geochemical characteristics of cave water to evaluate its origin and flow path. From June 2022 to may 2023, river water was collected at two sites (WE1 and WE2) in the Donggang River around Baengnyongdonggul Cave, and cave water was collected at four sites (WE3 to WE6) inside Baengnyongdonggul Cave. Water samples were analyzed for major dissolved components. Both river and cave waters were classified as Ca-HCO₃ type. All cave water samples were supersaturated in carbonate minerals, suggesting that carbonate minerals would precipitate within the cave. Due to differences in the source of cave water and the degree of water-rock interaction, the geochemical characteristics of water from sites where the flow of cave water is observed (WE3 and WE6) and rimstone pools (WE4 and WE5) could be clearly distinguished. The cave water at WE6 flows in from the Donggang River, then passes through WE3 and flows back out into the Donggang River. The cave water at WE4 and WE5 is supplied from precipitation, but the flow path of cave water at WE4 and WE5 is different.