• Applied Biological Chemistry
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• v.41 no.1
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• pp.89-94
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• 1998

Various Mn-oxides can oxidize Cr(III) to Cr(VI). Behaviors of chromium species in the oxidation system, especially on the oxide surface, are expected to control the reaction. During Cr(III) oxidation by birnessite and pyrolusite, Cr species in the reaction system were determined to elucidate their effects on the oxidation. Capacities of Cr oxidation of the two Mn-oxides were quite different. Solution pH and initial Cr(III) concentration also had significant effects on the Cr(III) oxidation by Mn-oxides. Chromium oxidation by pyrolusite was less than 5% of the oxidation by birnessite. The high crystallinity of pyrolusite could be one of the reasons and the difficulty of Cr (III) diffusion to the positive pyrolusite surface and Cr(VI) and Cr(III) adsorption seems to be other controlling factors. At pH 3, adsorption or precipitation of Cr species on the surface of birnessite were not found. Small amount of Cr(VI) adsorption was found on the surface of pyrolusite, but arty Cr precipitation on the oxide surface was not found. Therefore Cr(III) oxidation at pH 3 seems to be controlled mainly by the characteristics of Mn-oxides. Chromiun oxidation by Mn-oxides is thermodynamically more favorable at higher solution pH. However as solution pH increased Cr oxidation by birnessite was significantly inhibited. For Cr oxidation by pyrolusite, as pH increased the oxidation increased, but as Cr(III) addition increased the reaction was inhibited. Under these conditions some unidentified fraction of Cr species was found and this fraction is considered to be Cr(III) precipitation an the oxide surface. Chromium(III) precipitation on the oxide surface seems to play an important role in limiting Cr(III) oxidation by armoring the reaction surface on Mn-oxides as well as lowering Cr(III) concentration available for the oxidation reaction.

• Economic and Environmental Geology
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• v.38 no.6 s.175
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• pp.699-705
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• 2005

In order to identify the speciation of As and trace elements which are contained weathered waste rocks on the abandoned Jangpoong Cu mine area, five fraction sequential extraction was carried out. Concentrations of the extraction solutions which were acquaired each fraction were mesured by ICP-AES. Mineral characters of weathered waste rocks were determinated by XRD. The weathered waste rocks could divide into two types (Type I and type II). Type land type II weathered waste rocks are mainly composed of a quartz and a calcite, respectively. The most dominant speciation of As, Co and Fe is residual phase. Most of the speciation of Cd, Mn and Zn is residual phase for type I and Fe-Mn oxide phase for type II. In case of Cu, residual phase is predominant in type I and sulfide is predominet in type II. The most dominant speciation of Pb for type I and type II is associated with the residual phase and Fe-Mn oxide phase, respectively. At pH 4-7 range, the order of relative mobility considers Zn>Cu>Cd>Pb>Co>AS in type I, and Cd>Cu>Zn>Pb>As>Co in type II.

• Resources Recycling
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• v.30 no.5
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• pp.25-31
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• 2021

Smelting reduction of spent lithium-ion batteries results in the production of metallic alloys in which reduced cobalt, nickel and copper coexist. In this study, we investigated the leaching of the metallic alloys containing the above three metals together with iron, manganese, and silicon. The mixture of hydrochloric acid and hydrogen peroxide as an oxidizing agent was employed, and the effect of the concentration thereof, the reaction time and temperature, and pulp density was investigated to accomplish the complete leaching of cobalt, nickel, and copper. The effect of the hydrogen peroxide concentration and pulp density on the leaching was prominent, compared to that of reaction time and temperature, especially in the range of 20 to 80℃. The complete leaching of the metals present in metallic alloys, except silicon, was accomplished using 2 M HCl and 5% H₂O₂ with a pulp density of 30 g/L for 150 min at 60℃.

• Economic and Environmental Geology
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• v.34 no.3
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• pp.271-281
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• 2001

The characteristics of the heavy metal contamination in the soils affected by the tailings of the Palbong mine have been studied. The soils in the studied area consist mostly of loam by the particle size analysis, but a little of it, located near the stream, consist of loamy sand to sandy loam, finally to loam downward. The organic contents of soils are significantly low aoom 2 percent and the pH is in acidic ranging 6.0 $\pm$ 0.1. The samples of the parent rocks, the normal soils, the tailings and the channel deposits from the studied area were chemically analysed. From the result, the heavy metal concenlration of the soils is a little Jow compared with that of the parent rocks, shows the hydrologic process of the surface and the groundwater. The contamination of the tailings from the ore mining are high in lead, copper and arsenic. In the channel deposits the concenlrations of lead and copper are abnormally high but that of arsenic is uniquely low. And most of heavy metal contamination are decreased with the distance from the mine. It is caused by the properties of the surface and the ground water during the process of the heavy metal migration. The correlation-coefficient between sand and silt contents and the concentrations of Cd, Cu and Pb are significant but the amounts of As and Hg are increased with the clay contents. The dispersion of the heavy metals with the distance shows that the concentrations of them in the soils sampled at distance of 100 m to 200 m along the stream started near the Palbong mine are extremely high compared with those from other distances. These discrepancies are significant in Cd, Cu, Pb and Hg, but low in As. All the samples contain below detection limit of Cr+6 In the present stream water the concentrations of the heavy metals are not detected. So, it is interpreted that the concentrations in the soils are caused by the activities of the mining during the operation and have been continued by the dispersion from the tailings since after the closure of the mining, especially by the surface and ground water. The concentrations are diminished with the distance from the mining site, but in the interval of 800-2000 m increases abruptly. In the soil samples counted on the dispersion direction by wind, the lowering of the concentration is relatively uniform with the distance from the mining site. So, the rapid increase of the heavy metal concentrations is presumed to have been caused by the ground-water movement. In the migration of the heavy metals, the groundwater conditions, such as pH, Eh, the contents of colloidal particles, and Mn and Fe oxides are closely involveo. Integrating with these factors, it is interpreted that the groundwater conditions which have caused the heavy metal contamination of the studied area are those that the pH is about 3 in oxidized conditions, the contents of the colloidal particles are low, and Mn and Fe oxides are not involved in the migration of the heavy metals. Meanwhile, the vegetables growing on the soils in the studied area are not affected by the contamination of the heavy metals.

• 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.

• Journal of the Korean Magnetics Society
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• v.13 no.4
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• pp.155-159
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• 2003

We report on the annealing effect and ferromagnetic characteristics of Zn$_{0.7}$Mn$_{0.3}$O film prepared by sol-gel method on the silicon (100) substrate using field emission-scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), X-ray diffractometry (XRD) and superconducting quantum interference device (SQUID) magnetometry. Magnetic measurements show thatZn$_{0.7}$Mn$_{0.3}$O films exhibit ferromagnetism at 5 K revealing the coercive field of ∼110 Oe for as grown sample and 360, 1035 Oe for samples annealed at 700, 800 $^{\circ}C$, respectively. Our experimental evidence suggests that ferromagnetic precipitates of a manganese oxide may be responsible for the observed ferromagnetic behaviors of the film.he film.

• Journal of the Korean Chemical Society
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• v.53 no.1
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• pp.42-50
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• 2009

The dielectric-spectroscopic and ac conductivity studies firstly carried out on layered manganese doped Sodium Lithium Trititanates ($Na_{1.9}Li_{0.1}Ti_3O_7$). The dependence of loss tangent (Tan$\delta$), relative permittivity ($\varepsilon_r$) and ac conductivity ($\sigma_{ac}$) in temperature range 373-723K and frequency range 100Hz-1MHz studied on doped derivatives. Various conduction mechanisms are involved during temperature range of study like electronic hopping conduction in lowest temperature region, for MSLT-1 and MSLT-2. The hindered interlayer ionic conduction exists with electronic hopping conduction for MSLT-3. The associated interlayer ionic conduction exists in mid temperature region for all doped derivatives. In highest temperature region modified interlayer ionic conduction along with the polaronic conduction, exist for MSLT-1, MSLT-2, and only modified interlayer ionic conduction for MSLT-3. The loss tangent (Tan$\delta$) in manganese-doped derivatives of layered $Na_{1.9}Li_{0.1}Ti_3O_7$ ceramic may be due to contribution of electric conduction, dipole orientation, and space charge polarization. The corresponding increase in the values of relative permittivity may be due to increase in number of dipoles in the interlayer space while the corresponding decrease in the values of relative permittivity may be due to the increase in the leakage current due to the higher doping.

• Economic and Environmental Geology
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• v.38 no.5 s.174
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• pp.571-577
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• 2005

Permeable reactive barrier using iron oxide coated sand is one of effective technologies for As(V) contaminated groundwater. However, this method is restricted to As(III), because As(III) species tends to be more weakly bound to adsorbent. In order to overcome the limitation of iron oxide coated sand application to As(III) contaminated groundwater, manganese oxide materials as promoter of As(III) removal were combined to the conventional technology in this study. For combined use of iron oxide coated sand and manganese oxide coated sand, two kinds of removal methods, sequential removal method and simultaneous removal method, were introduced. Both methods showed similar removal efficiency over $85\%$ for 6 hrs. However, the sequential method converted the As contaminated water to acid state (pH 4.5), on the contrary, the simultaneous method maintained neutral state (pH 6.0). Therefore, simultaneous As removal method was ascertained as a suitable treatment technology of As contaminated water. Moreover, for more effective As(III) remediation technique, polypropylene textile which has the characteristics of high surface area, low specific gravity and flexibility was applied as alternative material of sand. The combined use of coated polypropylenes by simultaneous method showed much more prominent and rapid remediation efficiency over $99\%$ after 6 hrs; besides, it has practical advantages in replacement or disposal of adsorbent for simple conventional removal device.

• Economic and Environmental Geology
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• v.35 no.6
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• pp.553-565
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• 2002

Seasonal variations in vertical distributions of metals were investigated in the contaminated paddy soils around Siheung Cu-Pb-Zn and Deokeum Au-Ag mines. Geochemical behavior of metals was also evaluated with respect to redox changes during the cultivation of rice. Two microcosms simulating the rice-growing paddy field were set up in the laboratory. The raw paddy soils from two sites showed differences in mineralogy, metal concentrations and gecochemical parameters, and it is suggested that high proportions of exchangeable fractions in metals may give high dissolution rates at Deokeum. In both microcosms of Siheung and Deokeum, redox differences between surface and subsurface of paddy soils were maintained during the flooded period of 18 weeks. Siheung soil had neutral to alkaline pH conditions, while strongly acidic conditions and high Eh values were found at the surface soil of Deokeum. The concentrations of dissolved Fe and Mn were higher in the subsurface pore waters than in interface and upper waters from both microcosms, indicating reductive dissolution under reducing conditions. On the contrary, dissolved Pb and Zn had high concentrations at the surface under oxidizing conditions. From the Siheung microcosm, release of dissolved metals into upper waters was decreased. presumably by the trap effect of Fe- and Mn-rich layers at the interface. However, in the Deokeum microcosm, significant amounts of Pb and Zn were released into upper water despite the relatively lower contents in raw paddy soil, and seasonal variations in the chemical fractionation of metals were observed between flooded and drained conditions. Under acidic conditions, rice may uptake high amounts of metals from the surface of paddy soils during the flooded periods, and increases of exchangeable phases may also increase the bioavailability of heavy metals in the drained conditions.

• Journal of Soil and Groundwater Environment
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• v.10 no.4
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• pp.62-69
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• 2005

Removal of 4-chlorophenol (4CP) by natural manganese dioxide (NMD) catalyzed reaction was investigated in this study. Tests were also carried out to evaluate the effects of pH and natural organic matter (NOM) on the degradative oxidation of 4CP. Experimental results proved that NMD was effective for the removal of 4CP. Extensive kinetic analysis suggests that overall oxidation of 4CP by NMD is second-order reaction, the first-order with respect to 4CP, and the first-order with respect to NMD, respectively. Also, 4CP oxidation rates on the Mn-oxide surfaces were highly dependent upon experimental conditions such as pH, initial concentration of 4CP or NMD, and existence of humic acid. As pH increased above PZC of NMD, the reaction rate of 4CP was decreased, due to the low affinity of 4CP on NMD at high pH. At pH lower than PZC of NMD, reaction rate of 4CP was also decreased. It was considered that humic acid was involved in the oxidative coupling reaction of 4CP by NMD, resulting in the enhanced degradation rate of 4CP. This study proved that natural manganese oxide can be effectively applied for the removal of chlorophenols in aqueous phase.