• Economic and Environmental Geology
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• v.41 no.6
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• pp.673-683
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• 2008

As-rich alluvial groundwaters occurring in the agricultural area of Mankyeong River watershed were geochemically studied. 15 out of 29 investigated wells (52%) showed As levels exceeding the WHO drinking water standard ($10{\mu}g/L$). Their chemistry is characterized by low Eh levels, low $NO_3$ and $SO_4$ concentrations, and high pH, alkalinity, Fe, $NH_4$, and $PO_4$ levels. This suggests that arsenic is enriched by the reductive dissolution of As-bearing Fe-/Mn-(hydro)oxides, the commonest process in Bangladesh and West Bengal of India, of which groundwaters are severely contaminated by As. It was also revealed that As concentrations in the area are strongly regulated by the presence of agrochemicals such as $NO_3$ and $SO_4$.

• Journal of the Korean Chemical Society
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• v.35 no.3
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• pp.226-232
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• 1991

Adsorption and oxidation of polychlorinated phenols by suspended ${\sigma}-MnO_2$ in aqueous solution have been studied. Of the proposed mechanism, adsorption reaction of chlorophenols onto ${\sigma}-MnO_2$(s) depended upon the pH of the solution and the concentration of chlorophenol. Adsorption isotherms showed a reasonably good fit to the Langmuir isotherm. From the pH dependence of adsorption partition coefficient and the linear relationship between octanol-water partition coefficient and adsorption partiton coefficient of chlorophenol, it is estimated that adsorption is dominated by its hydrophobicity. The rate of electron transfer reaction evaluated from the rate of reductive dissolution of ${\sigma}-MnO_2$(s) depended linearly upon the concentration of chlorophenol and the pH of medium. Observed rate constants ($K_0$) of the meta-substituted chlorophenol were lower than that of the ortho-or para-chlorophenol because of resonance effect of chlorophenoxy radical. It is indicated that this radical is produced in the adsorption process and the electron transfer reaction is rate determining.

• Resources Recycling
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• v.13 no.1
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• pp.14-21
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• 2004

Spent catalysts containing platinum were generated in petroleum refinery and other chemical industries. The reclamation of platinum metals from such wastes has long been attempted in view of their rare, expensive and indispensable nature. In this study, the recovery of platinum from petroleum catalysts was attempted by a method consisting mainly of dissolving alumina carrier with sulfuric acid thereby concentrating insoluble platinum. Also, platinum dissolved partially in sulfuric acid was recovered by a cementation method using aluminum metal as a reductive agent. The effect of temperature, time, concentration of sulfuric acid, and pulp density on the dissolution of carrier was investigated. When the carrier of platinum catalyst was $\Upsilon-Al_2$O$_3$ about 95% alumina was dissolved in 6.0 M sulfuric acid at $100^{\circ}C$ for 2 hours. When the carrier was the mixture of $\Upsilon-Al_2$$O_3$ and $\alpha$-$Al_2$$O_3$ about 92% was dissolved after 4 hours. As a result, more than 99% of platinum could be recovered by this method and aluminum sulfate was also obtained as byproduct.

• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.714-722
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• 2019

Catalysts were prepared by using incipient wetness impregnation method with 17 wt% Ni on a support ($SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, $SiO_2$, $TiO_2$, MgO) and the catalytic activity in the reductive amination of ethanol with ammonia in the presence of hydrogen was compared and evaluated. The catalysts used before and after the reaction were characterized using X-ray diffraction, nitrogen adsorption, ethanol-temperature programmed desorption (EtOH-TPD), isopropanol-temperature programmed desorption (IPA-TPD), and hydrogen chemisorption etc. In the case of preparing $ZrO_2$ and $Y_2O_3$ supports, the small amount of Si dissolution from the Pyrex reactor surface provoked the formation of mixed oxides $SiO_2-ZrO_2$ and $SiO_2-Y_2O_3$. Among the catalysts used, $Ni/SiO_2-Y_2O_3$ catalyst showed the best activity, and this good activity was closely related to the highest nickel dispersion, and low desorption temperature in EtOH-TPD and IPA-TPD. The low catalytic activity on Ni/MgO catalysts showed low activity due to the formation of NiO-MgO solid-solutions. In the case of $Ni/TiO_2$, the reactivity was low due to the low nickel metal phase due to strong metal-support interaction. In the case of using a support as $SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, and $SiO_2$, the selectivities of ethylamines and acetonitrile were not significantly different at similar ethanol conversion.

• 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.

• Korean Journal of Microbiology
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• v.45 no.4
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• pp.411-415
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• 2009

Some microorganisms are capable of leaching Mn(II) from nonsulfidic manganese ores indirectly via nonenzymatic processes. Such reductive dissolution requires organic substrates, such as glucose, sucrose, or galactose, as a source of carbon and energy for microbial growth. This study investigated characteristics of Mn(II) leaching from manganese nodules by using heterotrophic Bacillus sp. strain MR2 provided with corn starch as a less-expensive substrate. Leaching of Mn(II) at 25.6 g Mn(II) $kg^{-1}$ nodule $day^{-1}$ was accompanied with cell growth, but part of the produced Mn(II) re-adsorbed onto residual $MnO_2$ particles after 24 h. Direct contact of cells to manganese nodule was not necessary as a separation between them with a dialysis tube produced similar amount [24.6 g Mn(II) $kg^{-1}$ nodule $day^{-1}$]. These results indicated an involvement of extracellular diffusible compound(s) during Mn(II) leaching by strain MR2. In order to optimize a leaching process we tested factors that influence the reaction, and the most efficient conditions were $25\sim35^{\circ}C$, pH 5~7, inoculum density of 1.5~2.5% (v/v), pulp density of 2~3 g/L, and particle size <75 ${\mu}m$. Although Mn(II) leaching was enhanced as particle size decrease, we suggest <212 ${\mu}m$ as a proper size range since more grinding means more energy consumption The results would help for the improvement of bioleaching of manganese nodule as a less expensive, energy-efficient, and environment-friendly technology as compared to the existing physicochemical metal recovery technologies.

• Economic and Environmental Geology
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• v.36 no.5
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• pp.349-356
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• 2003

As industrial activities are growing, pollutants found in the contaminated land are getting diverse. Some contaminated areas are subject to mixed wastes containing both organic and inorganic wastes such as hydrocarbon and heavy metals. This study concerns with the influence of the degradation of organic pollutants on the coexisting heavy metals, expecially for As. As mainly exists as two different oxidation state; As(III) and As(V) and the conversion between the two chemical forms may be induced by organic degradation in the soil contaminated by mixed wastes. We operated microcosm in an anaerobic chamber for 60 days, using sandy loam. The soils in the microcosm are artificially contaminated both by tetradecane and As, with different combination of As(III) and As(V); As(III):As(V) 1:1, As(III) only and As(V) only. Although not systematic, ratio of As(III)/As(Total) increase slightly at the later stage of experiment. Considering complicated geochemical reactions involving oxidation/reduction of organic materials, Mn/Fe oxides and As, the findings in the study seem to indicate the degradation of the organics is connected with the As speciation. That is to say, the As(V) can be reduced to As(III) either by direct or indirect influence induced by the organic degradation. Although Fe and Mn are good oxidising agent for the oxidation of As(III) to As(V), organic degradation may have suppressed reductive dissolution of the Fe and Mn oxides, causing the organic pollutants to retard the oxidation of As(III) to As(V) until the organic degradation ceases. The possible influence of organic degradation on the As speciation implies that the As in mixed wastes may be have elevated toxicity and mobility by partial conversion from As(V) to As(III).

• Economic and Environmental Geology
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• v.41 no.3
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• pp.327-334
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• 2008

Understanding the chemical characteristics of sediments and the nutrient diffusion from sediments to the water body is important in the management of surface water quality. Changes in chemical properties and nutrient concentration of a submerged soil were monitored for 6 months using a microcosm with the thickness of 30cm for upland soil and 15cm of water thickness above the soil. The soil color changed from yellowish red to grey and an oxygenated layer was formed on the soil surface after 5 week flooding. The redox potential and the pH of the pore water in the microcosm decreased during the flooding. The nitrate concentration of the surface water was continuously increased up to $8\;mg\;l^{-1}$ but its phosphate concentration decreased from $2\;mg\;l^{-1}$ to $0.1\;mg\;l^{-1}$ during flooding. However, the concentrations of $NH_4^+$, $PO_4^{3-}$, Fe and Mn in the pore water were increased by the flooding during this period. The increased $NO_3^-$ in the surface water was due to the migration of $NH_4^+$ formed in the soil column and the oxidation to $NO_3^-$ in the surface water. The increased phosphate concentration in the pore water was due to the reductive dissolution of Fe-oxide and Mn-oxide, which scavenged phosphate from the soil solution. The oxygenated layer played a role blocking the migration of phosphate from the pore water to the water body.

• Korean Journal of Environmental Agriculture
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• v.28 no.2
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• pp.165-170
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• 2009

The increase in P availability to rice under flooded soil conditions involves the reductive dissolution of iron phosphate and iron (hydr)oxide phosphate. However, since $NO_3^-$ is a more favourable electron acceptor in anaerobic soils than Fe, high$NO_3^-$ loads function as a redox buffer limiting the reduction of Fe. The effect of adding $NO_3^-$ on Fe reduction and P release in paddy soil was investigated. Pot experiment was conducted where $NO_3^-$ was added to flooded soil and changes of redox potential and $Fe_2^+$, $NO_3^-$ and $PO_4^{3-}$ concentrations in soil solution at 10 cm depth were monitored as a function of time. Redox potential decreased with time to -96 mV, but it was temporarily poised at about 330${\sim}$360 mV when $NO_3^-$ was present. Nitrate addition to soil led to reduced release of $Fe_2^+$ and prevented the solubilization of P. Phosphate in pore water began to rise soon after incubation and reached final concentrations about 0.82 mg P/L in the soil without $NO_3^-$ addition. But, in the soil with $NO_3^-$ addition, $PO_4^{3-}$ in pore water was maintained in the range of 0.2${\sim}$0.3 mg P/L. The duration of inhibition in $Fe_2^+$ release was closely related to the presence of $NO_3^-$, and the timing of $PO_4^{3-}$ release was inversely related to the $NO_3^-$ concentration in soil solution. The results suggest that preferential use of $NO_3^-$ as an electron acceptor in anaerobic soil condition can strongly limit Fe reduction and P solubilization.

• Economic and Environmental Geology
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• v.42 no.6
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• pp.599-608
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• 2009

This study was conducted to examine chemical characteristics and correlations among seepage water, subsurface waters and inland groundwater in and around a coastal underground LPG cavern using factor and cluster analyses. The study area is located in western coast of Incheon metropolitan city and is about 8 km off the coast. The LPG cavern storing propane and butane was built beneath artificially reclaimed island. Mean bathymetry is 8.5 m and maximum sea level change is 10 m. Water sampling was conducted in May and August, 2006 from 22 sampling points. Correlation analysis showed strong correlations among $Fe^{2+}$ and $Mn^{2+}$ (r=0.83~0.99), and Na and Cl (r=0.70~0.97), which indicated reductive dissolution of iron and manganese bearing minerals and seawater ingression effect, respectively. According to factor analysis, Factors 1 (May) and I (August) showed high loadings for parameters representing seawater ingression into the cavern and effect of submarine groundwater discharge, respectively while Factors 2 and IV showed high loadings for those representing oxidation condition (DO and ORP). Factors 4 and II have large positive loadings for $Fe^{2+}$ and $Mn^{2+}$. The increase of $Fe^{2+}$ and $Mn^{2+}$ was related to decomposition of organic matter and subsequent their dissolution under reduced condition. Cluster analysis showed the resulting 6 groups for May and 5 groups for August, which mainly included groups of inland groundwater, cavern seepage water, sea water and subsurface water in the LPG storage cavern. Subsurface water (Group 2 and Group III) around the underground storage cavern showed high EC and major ions contents, which represents the seawater effect. Cavern seepage water (Group 5 and Group II) showed a reduced condition (low DO and negative ORP) and higher levels of $Fe^{2+}$ and $Mn^{2+}$.