• Environmental Engineering Research
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• v.25 no.4
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• pp.529-535
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• 2020

The present study investigated the photodegradation of synthetic organic dye; violet-3B, without and with the addition of C-N-codoped TiO₂ catalyst using a visible halogen-lamp as a light source. The catalyst was synthesized by using a peroxo sol-gel method with free-organic solvent. The effects of initial dye concentration, catalyst dosage, and pH solution on the photodegradation of violet-3B were examined. The efficiency of the photodegradation process for violet-3B dye was higher at neutral to less acidic pH. The kinetics reaction rate of photodegradation of violet-3B dye with the addition of C-N-codoped TiO₂ followed pseudo-first order kinetics represented by the Langmuir-Hinshelwood model, and increasing the initial concentration of dyes decreased rate constants of photodegradation. Photodegradation of 5 mg L^-1 violet-3B dye achieved 96% color removal within 240 min of irradiation in the presence of C-N-codoped TiO₂ catalyst, and approximately 44% TOC was removed as a result of the mineralization.

• Journal of Pharmaceutical Investigation
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• v.23 no.4
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• pp.225-229
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• 1993

The stability of omeprazole in the aqueous solutions containing arginine or sodium phosphate dibasic(SPD) was examined at 30, 40 and $50^{\circ}C$. Arginine or anhydrous SPD was added to omeprazoie solution ($200{\mu}g/\;ml$ in distilled water) to yield $100{\mu}g/\;ml$ concentration of each. Then, the solution was kept at 30, 40 or $50^{\circ}C$ for 90 hrs. Aliquots of the solution were withdrawn at specified time intervals and assayed by HPLC for intact omeprazole. The remaining percentage-time curves revealed that omeprazole was degraded rapidly as funtions of time and temperature following pseudo first-order kinetics. The rate constant in the SPD solution was much higher than in the arginine solution. In other words. the degradation half-lives of omeprazole at $30^{\circ}C$, for example, was 148 and 76 hr in arginine and SPD solutions respectively. The initial pH of the solution containing $100{\mu}g/\;ml$ of arginine or SPD was 9.7 or 8.7, respectively. Since omeprazole is more stable as the pH of its solution becomes more alkaline, the longer half-life of omeprazole in arginine solution could be explained by the more alkaline characteristics of arginine than SPD in the solution. The activation energy necessary for the degradation reaction was almost identical in both solutions, indicating similar degradation mechanisms of omeprazole in the solutions. In conclusion, omprazole was more stable in the presence of arginine than of SPD.

• Journal of Soil and Groundwater Environment
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• v.21 no.2
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• pp.8-14
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• 2016

We compared the plausible reaction mechanism and quantitative efficiency of highly self-organized TiO₂ nanotube (ntTiO₂) film with TiO₂ powder. Film was fabricated by electrochemical potentiostatic anodization of titanium thin film in an ethylene-glycol electrolyte solution containing 0.3 wt% NH₄F and 2 vol% deionized water. Nanotubes with a pore size of 80-100 nm were formed by anodization at 60 V for 3 h. Humic acid (HA) was degraded through photocatalytic degradation using the ntTiO₂ film. Pseudo first-order rate constants for 0.3 g of ntTiO₂, 0.3 g TiO₂ powder, and 1 g TiO₂ powder were 0.081 min⁻¹, 0.003 min⁻¹, and 0.044 min⁻¹, respectively. HA adsorption on the ntTiO₂ film was minimal while adsorption on the TiO₂ powder was about 20% based on thermogravimetric analysis. Approximately five-fold more normalized OH radicals were generated by the ntTiO₂ film than the TiO₂ powder. These quantitative findings explain why ntTiO₂ film showed superior photocatalytic performance to TiO₂ powder.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1166-1172
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• 1997

[FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

• Resources Recycling
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• v.17 no.6
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• pp.34-42
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• 2008

The properties of sodium silicate solution were surveyed by using the yellow silicomolybdic method, and the formation of silica sol from sodium silicate solution and the growth of silica sol were investigated in this study. The $SiO_2$ content of 2 wt% in sodium silicate solution was proper to oxidize sodium silicate with sulfuric acid. After the removal of sodium ions in sodium silicate solution, the pH of silicate solution had to be controlled above 9 for the stabilization of silicate solution. The condensation between silicic acid species and silica nuclei surfaces has been studied at $20{\sim}80^{\circ}C$ and pH 10 in silicate solutions with silica nuclei. The reaction falls into two kinetics regimes, limited at high silicic acid species concentration by polymerization, but at lower concentration by a process whereby deposited silicic acid species condenses further to silica. The overall condensation is first-order in silicic acid species concentration, proceeded toward to pseudo equilibrium concentration, $C_x$, rather than the solubility of amorphous silica. The heat of solution of amorphous silica was 3.34 kcal/mol and exhibits an Arrhenius temperature dependence with an apparent activation energy of 3.16 kcal/mol in the range of $20{\sim}80^{\circ}C$.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.6
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• pp.547-554
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• 2010

In this study, new manganese oxide (i.e., black-birnessite) particles with nanostructures were prepared and its physico-chemical properties and oxidative-transformation efficiency on 1,4-naphthoquinine(1,4-NPQ) in the presence of reactive mediator was investigated. The results were also compared with that of the manganese oxide (i.e., brown-birnessite) particles synthesized by classical McKenzie method. Analysis of XRD and SEM data show that the particles are a single phase corresponding to a birnessite-based manganese oxide with cotton ball-like shapes containing nanofibers. In batch experiments, removals of 1,4-NPQ by the black-birnessite follows pseudo-first-order kinetics and the rate constant values obtained are greater about 2.3 times than that of the brown-birnessite in spite of its lower surface area (41.0 vs 19.80 $m^2/g$). The results can be explained by the higher crystallinity and nano structured features of the back-birnessite particles, which give higher reactivity for the removals of the quinone compound. HPLC analysis of the reaction products confirmed that the balck-birnessites removed 1,4-NPQ through cross-coupling reaction in the presence of catechol as a reactive mediator.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.3
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• pp.186-192
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• 2009

In this study, The effects of three different activated carbon materials (each coal, coconut and wood based activated carbons), empty bed contact time (EBCT) and water temperature on the removal of pharmaceutical 4 species (oxytetracycline, tetracycline, trimethoprime and caffeine) in BAC filters were investigated. Experiments were conducted at three water temperature (5, 15 and $25^{\circ}C$) and four EBCTs (5, 10, 15 and 20 min). The results indicated that coal based BAC retained more attached bacterial biomass on the surface of the activated carbon than the other BAC, increasing EBCT or increasing water temperature increased the pharmaceutical 4 species removal in BAC columns. In the coal-based BAC columns, removal efficiencies of oxytetracycline and tetracycline were 87~100% and removal efficiencies of trimethoprime and caffeine were 72~99% for EBCT 5~20 min at $25^{\circ}C$. The kinetic analysis suggested a firstorder reaction model for pharmaceutical 4 species removal at various water temperatures (5~$25^{\circ}C$). The pseudo-first-order reaction rate constants and half-lives were also calculated for pharmaceutical 4 species removal at 5~$25^{\circ}C$. The reaction rate and half-lives of pharmaceutical 4 species ranging from 0.0360~0.3954 $min^{-1}$ and 1.75 to 19.25 min various water temperatures and EBCTs, could be used to assist water utilities in designing and operating BAC filters.

• Applied Chemistry for Engineering
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• v.31 no.2
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• pp.164-171
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• 2020

Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich's equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (R_L = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (R_L = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich's equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△H_x = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△H_x < 80 kJ/mol).

• Journal of Korean Society of Environmental Engineers
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• v.31 no.4
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• pp.278-286
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• 2009

In this study, four natural Mn oxides ($NMO_1-NMO_4$) was characterized using x-ray diffraction, scanning electron microscopy, and their removal efficiency for 1-naphthol (1-NP) in aqueous phase, using batch reactor, was investigated. The results were compared with one another and a synthetic manganese oxide, birnessite. The NMOs have a various Mn minerals including pyrolusite (${\beta}-MnO_2$), cryptomeltane (${\alpha}-MnO_2$) as well as birnessite (${\delta}-MnO_2$) depending on their sources, which results in different removal efficiencies (removals, kinetics) and reaction types (sorption or oxidative-transformation). The comparative study showed that $NMO_1$ (electrolytic Mn oxide) have a higher removal efficiency for 1-NP via oxidative-transformation compared to birnessite. The 1-NP removals by NMOs were followed by pseudo-first order reaction, and the surface area-normalized specific rate constants ($K_{surf},\;L/m^2$ min) determined were in order of $NMO_1(3.31{\times}10^{-3})$>${\delta}-MnO_2(1.48{\times}10^{-3}){\fallingdotseq}NMO_3(1.46{\times}10^{-3})$>$NMO_2(0.83{\times}10^{-3})$>$NMO_4(0.67{\times}10^{-3})$. From the solvent extraction experiments with the Mn oxide precipitates after reaction, it was observed that the oxidative-transformation rates of 1-NP were in order of $NMO_1{\fallingdotseq}{\delta}-MnO_2$>$NMO_3$>$NMO_4{\gg}NMO_2$ and the analysis of HPLC chromatogram and UV-Vis. absorption ratios ($A_{2/4}$, $A_{2/6}$) on the supernatant confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Results from this study proved that natural Mn oxide (except $NMO_2$) used in this experiment can be effectively applied for the removal of naphthols in aqueous phase, and the removal efficiencies are depending on the surface characters of the Mn oxides.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.11
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• pp.989-996
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• 2009

In this study, the effects of biofilter media type (three different activated carbons and anthracite), empty bed contact time (EBCT) and temperature on the removal of four aldehyde species (formaldehyde, acetaldehyde, glyoxal and methylglyoxal) in BAC filters were investigated. Experiments were conducted at three water temperature (5, 15 and $25^{\circ}C$) and four EBCTs (5, 10, 15, and 20 min). The experimental results indicated that the coal based BAC retained more bacterial biomass on the surface of the activated carbon than the other BACs, and increasing EBCT or increasing water temperature also increased the four aldehyde species removal in BAC filters. To achieve above 80% of removal efficiency for four aldehyde species in a BAC filter, above 15 min EBCT at $5^{\circ}C$ and 10 min EBCT at above $15^{\circ}C$ were required. The kinetic analysis indicated a first-order reaction rate for the biodegradation of four aldehyde species at various water temperatures. Data obtained from the BAC filters at various temperatures were also used to evaluate pseudo first-order rate constants for four aldehyde species. The half-lives evaluated for formaldehyde, acetaldehyde, glyoxal and methylglyoxal in the coal-based BAC ranging from 0.89 to 3.19 min, from 0.75 to 3.35 min, from 2.16 to 4.72 min and from 1.49 to 3.86 min, respectively, could be used to assist water utilities in designing and operating BAC filters.