• Applied Chemistry for Engineering
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• v.30 no.6
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• pp.749-756
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• 2019

Na-X and Na-A zeolites that give high adsorption capacity for heavy metals in an aqueous system were synthesized from the coal fly ash obtained from a thermoelectric power plant using a fusion method. The characteristics and Cu(II) adsorption capacity of the synthetic zeolites were also compared to those of using a commercial zeolite. For the selection of optimum conditions of zeolite synthesis, the effects of major parameters in the fusion method such as a dosage ratio of NaOH, aging time, hydrothermal reaction time, and also the dosage ratio of NaAlO₂ (Na-A) on the characteristics and Cu(II) adsorption capacity of the synthetic zeolites were studied. For the analysis of characteristics of the synthetic zeolites, X-ray diffraction (XRD), cation exchange capacity (CEC), Brunaue-Emmett-Teller (BET) and scanning electron microscopy (SEM) were used. The optimum conditions for the synthesis of zeolites with a high adsorption capacity for cationic heavy metals including Cu(II) were the aging time of 6 h, hydrothermal reaction time of 6 h and NaOH and NaAlO₂ dosage ratio of 1.5 and 0.5 (Na-A), respectively. According to the Langmuir isotherm test, maximum Cu(II) adsorption capacities of the synthetic and commercial Na-X and Na-A zeolites were found to be 90.1, 105.26, 102.05, and 109.89 mg/g, respectively. This indicates that the adsorption capacity of synthetic zeolites was comparable to commercial ones. The results of this study also suggest that the coal fly ash can be potentially used as a raw material for the zeolite synthesis.

• Economic and Environmental Geology
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• v.36 no.5
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• pp.375-380
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• 2003

This study was carried out 1) to investigate the pH effect on solubilization of phenanthrene by biosurfactant in aqueous system and 2) to evaluate the pH effect on the biodegradation rate of phenanthrene in the presence and the absence of the biosurfactant by phenanthrene degraders. Tween 80, which is a chemically synthesized surfactant, showed greater solubilizing capacity than rhamnolipid. The solubilization capacity can be expressed as a MSR(molar solubilization ratio=moles of organic compounds solubilized per mole of surfactant). The calculated MSR of Tween 80 and rhamnolipid were 0.1449 and 0.0425 respectively. The kinetic study of phenanthrene solubilization by rhamnolipid showed that solubilization mechanism could reach equilibrium within 24 hours. Addition of 240 ppm rhamnolipid solution, which concentration is 4.3 times of Critical Micelle Concentration(CMC), caused 9 times solubility enhancement compared to water solubility. The highest solubilities were detected around a pH range of 4.5-5.5. Changes in apparent solubility with the changes in pH are possibly related to the fact that the rhamnolipid, an anionic surfactant, can form different structures depending on the pH. Two biodegradation experiments were performed in the absence and the presence of rhamnolipid, with the cell growth investigated using a spread plate method. The specific growth rates at pH 6 and 7 were higher than at the other pH, and the HPLC analysis data, for the total phenanthrene loss, confirmed the trends in the $\mu$(specific growth rate) values. In presence of rhamnolipid, maximum $\mu$ values shifted from around pH 5 which showed maximum enhancement of solubility in the abiotic experiment, compared to the $\mu$ values obtained without the biosurfactant. In this study, the increase in the observed specific grow rate(1.44 times) was not as high as the increase in solubilization(5 times). This was supported by the fact all the solubilized phenanthrene is not bioavailable to microorganisms.

• Economic and Environmental Geology
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• v.41 no.6
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• pp.685-693
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• 2008

The rates of oxidative degradation of perchloroethene (PCE) and trichloroethene (TCE) using $KMnO_4$ solution were evaluated under the flow condition using a bench-scale transport experimental setup. Parameters which are considered to affect the reaction rates tested in this study were the contact time (or retention time), and the concentration of oxidizing agent. A glass column packed with coarse sand was used for simulating the aquifer condition. Contact time between reactants was controlled by changing the flow rate of the solution through the column. The inflow concentrations of PCE and TCE were controlled constant within the range of $0.11{\sim}0.21\;mM$ and $1.3{\sim}1.5\;mM$, respectively. And the contact time was $14{\sim}125$ min for PCE and $15{\sim}36$ min for TCE. The $KMnO_4$ concentration was controlled constant during experiment in the range of $0.6{\sim}2.5\;mM$. It was found that the reduction of PCE and TCE concentrations were inversely proportional to the contact time. The exact reaction order for the PCE and TCE degradation reaction could not be determined under the experimental condition used in this study. However, the estimated reaction rate constants assuming pseudo-1st order reaction agree with those reported based on batch studies. TCE degradation rate was proportional to $KMnO_4$ concentration. This was considered to be the result of using high inflow concentrations of reactant, which might be the case at the vicinity of the source zones in aquifer. The results of this study, performed using a dynamic flow system, are expected to provide useful information for designing and implementing a field scale oxidative removal process for PCE/TCE-contaminated sites.

• Economic and Environmental Geology
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• v.50 no.6
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• pp.435-443
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• 2017

The Hanae deposit is located within the Cretaceous Gyeongsang Basin. The Cu-bearing hydrothermal quartz vein formed by narrow open-space filling along fracture in the sedimentary rocks as Jindong Formation. The Hanae Cu-bearing hydrothermal deposit shows a paragenetic sequence of pyrrhotite-pyrite $\rightarrow$ pyrite-chalcopyrite-sphalerite(${\pm}$Bi-bearing tellurides) $\rightarrow$ Ag-bearing telluride mineralization $\rightarrow$ secondary mineralization. Fluid inclusion data indicate that the Hanae Cu-bearing hydrothermal mineralization occurred from dominantly aqueous fluids at temperatures of $400^{\circ}C-200^{\circ}C$. Equilibrium thermodynamic interpretation of the mineral paragenesis and assemblages combined with fluid inclusion data indicate that early main Cu-bearing ore mineralization in the vein starts at about $350^{\circ}C$ which corresponds to sulfur fugacity from about $10^{-9.2}$ to $10^{-8.7}bar$ with oxygen fugacity of about $10^{-32.1}$ to $10^{-29.8}bar$. Late main Cu-bearing ore mineralization in the vein occurs at about $250^{\circ}C$ which corresponds to sulfur fugacity from about $10^{-13.5}$ to $10^{-11.7}bar$ with oxygen fugacity of about $10^{-38.4}$ to $10^{-35.2}bar$. The late Ag-bearing telluride mineralization in the Hanae hydrothermal system occurs at about $200^{\circ}C$ which corresponds to minium Tellirium fugacity value of about $10^{-18}bar$ with sulfur fugacity of about $10^{-14.0}$ to $10^{-10.9}bar$.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.273-280
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• 1989

The spectra of the $Co^{II}CyDTA$(CyDTA: cyclohexyldiaminetetraacetic acid) complex have been measured in aqueous solution of pH = 6-13.2. The red shift of the spectrum in the more basic solution was ascribed to the transformation of $CoCyDTA^{2-}$ into $CoCyDTA(OH)^{3-}$. The equilibrium constant, $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$ was $75M^{-1}$ at $40^{\circ}C$. The electron transfer reactions of $CoCyDTA^{2-}$ and $CoCyDTA(OH)^{3-}$ with $Fe(CN)_6^{3-}$ have been studied using spectrophotometric technique in the range of pH applied to the determination of equilibrium constant. The pseudo first-order rate constants observed ($k_{obs}$) were not changed upto pH = 10.8, but increased with increasing pH in the range of pH = $10.8{\sim}13.0$. The rate law reduced in the range of pH = 6-13 was $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$. The rate constants of the reactions (3a) and (3b), $k_3$ and $k_4$ respectively have been determined to be 0.529 and $4.500M^{-1}sec^{-1}$ at $40^{\circ}C$. The activation entropies (147{\pm}1.1JK^{-1} mol^{-1}$ at pH = 10.8) and activation volumes $(6.25cm^3mol^{-1}, pH = 10.8)$ increased with increasing pH, while the activation enthalpy (12.44 ${\pm}$ 0.20 kcal/mole) was independent of pH. Using the pH effect on the rate constants, the activation entropies and the activation volumes, the mechanism of the electron transfer reaction for $Co^{II}-Fe^{III}$ system was discussed.

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.206-214
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• 2005

Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

• Applied Microscopy
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• v.37 no.1
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• pp.23-33
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• 2007

The lacrimal gland are compound tubule-acinar glands. The main lacrimal function is the production of the aqueous layer, the thickest and major constituent of the precorneal tear film. The lacrimal gland also has an important function in the defense system of the ocular surface, forming a part of the conjunctival-associated hymphoid tissue. The ultrastructural characteristics of the lacrimal gland of the rabbit were described. The lacrimal tissues of rabbits were processed through the conventional techniques for transmission electron microscopy. The secretory portions consisted of three cell types: 1. Serous cells with electron dense secretory granules. 2. Seromucous cells containing variable moderately electron dense secretory granules with flocculent material. 3. Mucous rolls containing mucous secretory granules. The serous cells were situated at the basal portion of acini, and they contained electron dense granules of variable densities and sizes. The seromucous cells contained a few protein secretory granules and more mucous secretory granules. The mucous cells contained even fewer protein secretory granules and exclusively mucous secretory granules. The epithelium of the intralobular ducts showed secretory granules, junctional complexes, and large basolateral intercellular spaces with lateral folds. These study might be helpful in determining inter-relationships, similarities and differences among the orbital glands of various physiological or pathological conditions.

• Economic and Environmental Geology
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• v.25 no.4
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• pp.397-416
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• 1992

In the present study, three clay deposits, named the Seongsan, Ogmaesan and Haenam deposits, were investigated. The altered zones are recognized in the hydrothermally altered rocks of the clay deposits from the center of the alteration to the margin: Kaolin, Kaolin-Quartz, Quartz, Sericite and Chlorite zones in the Seongsan deposits; Quartz zone, Alunite zone, Kaolin zone, Sericite zone and Chlorite zone in the Ogmaesan deposits; Quartz zone, Pyrophyllite zone, Sericite zone and Chlorite zone in the Haenam deposits. These zones can be grouped into two types of alteration: Acidic alteration such as Pyrophyllite zone, Alunite zone, Quartz zone, Kaolin zone, Kaolin-Quartz zone and a part of Sericite zone; Propylitic alteration such as Chlorite zone and a part of Sericite zone. All clay deposits belong to high-sulfidation (acid-sulfate) system. The rocks of the acidic alterations are composed of pyrophyllite, alunite, kaolin minerals, sericite, quartz and pyrite. On the basis of bulk chemical compositions, it was found that some components such as $SiO_2$, $TiO_2$, $Fe_2O_3$, FeO, MgO, CaO, $K_2O$ and $Na_2O$ were mobilized considerably from the original rocks. The mobility of these major elements is related to, and controls, mineral assemblages in each altered zone. Polytypes of sericite are determined as $2M_1$ and 1M by X-ray diffraction method. The amount of $2M_1$ is nearly equal to that of 1M in the Seongsan deposits whereas $2M_1$ is less and higher than that of 1M in the Ogmaesan and the Haenam deposits. These facts indicate that formation temperature of sericite is relatively high in the Haenam deposits, moderate in the Seongsan deposits, and low in the Ogmaesan deposits. The ratios of Na/(K+Na) for alunite in the Ogmaesan deposits determined by electron microprobe analyzer (EPMA) are higher than those in the Seongsan deposits. Thus, the alunite of the Ogmaesan deposits must have been formed from the solutions with relatively high aqueous Na/(K+Na) ratios and low pH at a high temperature rather than that of the Seongsan deposits. From all data, it is clarified that alunite is hypogene in origin, and has been formed by oxidation of hydrogen sulfide in the steam-heated environment, and that alunite has been produced by the spectacular solfataric alteration observed at the surface of some present-day hydrothermal systems.

• Clean Technology
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• v.28 no.1
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• pp.38-45
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• 2022

CuCl₂-loaded V₂O₅-WO₃/TiO₂ catalyst showed excellent activity in the catalytic oxidation of elemental mercury to oxidized mercury even under SCR condition in the presence of NH₃, which is well known to significantly inhibit the oxidation activity of elemental mercury by HCl. Moreover, it was confirmed that, when SO₂ was present in the reaction gas together with HCl, excellent elemental mercury oxidation activity was maintained even though CuCl₂ supported on the catalyst surface was converted to CuSO₄. This is thought to be because not only HCl but also the SO₄ component generated on the catalyst surface promotes the oxidation of elemental mercury. However, in the presence of SO₂, the total mercury balance before and after the catalytic reaction was not matched, especially as the concentration of SO₂ increased. In order to understand the cause of this, further studies are needed to investigate the effect of SO₂ in the SnCl₂ aqueous solution employed for mercury species analysis and the effect of sulfate ions generated on elemental mercury oxidation. It was confirmed that SO₂ also promotes NO_x removal activity, which is thought to be because the increase in acid sites by SO₄ generated on the catalyst surface by SO₂ facilitates NH₃ adsorption. The composition change and structure of the components present on the catalyst surface under various reaction conditions were measured by XRD and XRF. These measurement results were presented as a rational explanation for the results that SO₂ enhances the oxidation activity of elemental mercury and the NO_x removal activity in this catalyst system.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.303-312
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• 2023

The determination of the oxidation states of metal elements in manganese nodules sheds light on the understanding of the formation mechanism of nodules, providing insights into the paleo-environmental conditions such as the redox potential of the aqueous system. This study aims to reveal the oxidation states and chemical bonding of manganese in the natural polymetallic nodules, utilizing conventional X-ray photoelectron spectroscopy (XPS). Specifically, shallow manganese nodules from the Siberian Arctic Sea, effectively recording mineralogical variations, were used in this study. Detailed analysis of XPS Mn 2p spectra showed changes in the manganese oxidation state from the center to the outer parts of the nodules. The central part of the nodules showed a higher Mn⁴⁺ content, approximately 67.9%, while the outermost part showed about 63% of Mn⁴⁺ due to an increase in the Mn³⁺+Mn²⁺. The decrease in the Mn oxidation state with the growth is consistent with the previously reported mineralogical variations from todorokite to birnessite with growth. Additionally, the O 1s spectra presented a predominance of Mn-O-H bonds in the outer layers compared to the center, suggesting hydration by water in the layered manganates of outer layers. The results of this study demonstrate that XPS can be directly applied to understand changes in paleo-environmental conditions such as the redox states during the growth of manganese nodules. Finally, future studies using high-resolution synchrotron-based XPS experiments could achieve details in oxidation states of manganese and trace metal elements.