• Journal of Korean Society for Atmospheric Environment
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• v.33 no.2
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• pp.87-96
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• 2017

In this study, 4 gases containing typical chlorinated volatile organic compounds (VOCs) were treated by ultraviolet (UV) irradiation. The typical chlorinated VOCs are dichloromethane (DCM), trichloromethane (TCM), carbon tetrachloride (CTC) and trichloroethylene (TCE). The removal efficiency (RE) and the products of chlorinated VOCs by UV irradiation are investigated. At this time, 2 types of background gas (air and nitrogen) were used to figure out the RE by photooxidation and photolysis. The specification of UV-lamp used in this study was low-pressure mercury lamp emitting wavelength of 185~254 nm. The experimental conditions were set as initial VOC concentration of $180{\pm}10ppm$, empty bed retention time (EBRT) of 53 s, temperature of $23{\pm}2^{\circ}C$ and relative humidity of $65{\pm}5%$. In the photolysis condition with nitrogen ($N_2$) as background gas, the averaged RE of the 4 types of chlorinated VOCs was about 24% higher than that with photooxidation; and the REs of VOCs except CTC were confirmed as >99%. The composition of off-gases after UV photooxidation in air was investigated and several intermediates from DCM, TCM and TCE were detected by GC/MS. Among them, phosgene which is a toxics was detected as an intermediate of TCM. In addition, the concentration of carbon dioxide ($CO_2$) in the off-gases was measured to calculate the mineralization rate (MR). With the photooxidation, TCE showed the highest RE (>99%) while MR was the lowest (17%); and the MR of DCM was the highest (86%). In addition, particulate matters (PM) in the off-gases was also detected and high concentrated $PM_{10}$ ($21,580{\mu}g{\cdot}m^{-3}$) and $PM_{2.5}$ ($6,346{\mu}g{\cdot}m^{-3}$) were detected in TCE off-gas. More than 99% of the chlorinated VOCs could be removed using UV254-185 nm lamp, while it is necessary to conduct further studies on the production and treatment of secondary pollutants.

• Applied Biological Chemistry
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• v.43 no.2
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• pp.130-135
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• 2000

Photodegradation rate of flupyrazofos in aqueous solution were measured under various test conditions mainly following the guidelines of U.S. EPA and OECD. It was observed that the flupyrazofos was degraded by simple hydrolysis but not degraded by light in pure water. Using acetone as a known photosensitizer, the minimal concentration of acetone needed to photo-degrade the flupyrazofos in % and molar terms were 0.047% and 0.006, respectively. When treated with acetone, it was also found that the ringlet oxygen is a very effective photo oxidant in the degradation of flupyrazofos, but the effect of hydroxyl radical was not observed at the treatment level of hydroxyl radical, isopropylbenzene. In an actinometer experiment, quantum yield of flupyrazofos (0.4 ppm with 2% acetone) was $17.66{\times}10^{-5}$ and degradation rate and half-life were 0.038/hr and 18.2 hours, respectively.

• Particle and aerosol research
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• v.4 no.1
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• pp.9-20
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• 2008

The effect of light intensity on the ozone formation and the aerosol number concentration during the photochemical reactions of ambient air was investigated in an indoor smog chamber. The smog chamber consists of a housing, 64 blacklights, and a $2.5-m^3$ reaction bag made of Teflon film. The bag was filled with the unfiltered ambient air in Seoul from January 10 to March 18, 2002. In this work, the photolysis rate of $NO_2$, $k_1$ was used as an index of light intensity. Three levels of light intensity were controlled by changing the number of blacklights turned on among 64 blacklights: $0.29min^{-1}$ (50%), $0.44min^{-1}$ (75%), $0.57min^{-1}$ (100%). The ozone concentration increased rapidly within 10 minutes after irradiation irrespective of light intensity, thereafter it increased linearly during the irradiation. The ozone production rate seems to be dependent on both the light intensity and the quality of ambient air introduced into the reaction bag. The change in aerosol number concentration also depended on both the light intensity and the ambient air quality, especially aerosol size distribution. Based on the initial ambient aerosol size distributions, the photochemical potential for aerosol formation and growth is classified into two cases. One is the case showing aerosol formation and growth processes, and the other is the case showing no apparent change in particle size distribution.

• Clean Technology
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• v.23 no.1
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• pp.54-63
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• 2017

Volatile organic compounds (VOCs) are widely used in both industrial and domestic activities. VOCs are one of the most unpleasant, frequently complaint-rousing factors of pollution around the world. It is now necessary to research and develop an alternative technology that could overcome the problems of the existing odor-control and VOC-eliminating techniques. In this study, essential oil and photocatalytic process was applied in the removal of benzene and toluene, typical VOCs in petrochemistry plant. therefore, this study conducted experiments on the selection of appropriate essential oil, photodegradation, hydroxyl radical generation capacity. The removal efficiency and reaction rate were performed to selecte the type and concentration of essential oil. As a result, removal efficiency of Hinoki Cypress oil was approximately 70% and reaction rate of Hinoki Cypress was high. The results of photolysis experiment, photocatalytic oxidation process showed that the decomposition efficiency of VOCs increased considerably with increasing UV lamp power. In addition, the conversion of VOCs was increased up to $0.1gL^{-1}$ photocatalysts. The hydroxyl radicals measure was performed to determine the ability to generate hydroxyl radicals. The analytical result showed that high $TiO_2$ concentration and lamp power was produced many hydroxyl radical. Experiments of the removal efficiency and reaction rate were performed using essential oil and photooxidation. As a result, the removal efficiency showed that the removal efficiency was increased high temperature and reaction time. The activation energy was calculated from the reaction rate equation at various temperature condition. Activation energy was approximately $18kJmol^{-1}$.

• Journal of the Korean Chemical Society
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• v.27 no.3
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• pp.201-207
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• 1983

The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

• Journal of Photoscience
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• v.9 no.2
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• pp.308-310
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• 2002

Bacteriorhodopsin (bR) and halorhodopsin (hR), which exist in the membrane of Halobacterium salinarum, are light-driven ion pumps. In spite of high similarity of primary and tertiary structures between bR and hR, these membrane proteins transport different ions, proton and chloride, in the opposite direction. From alignment of the amino acid sequences, Thr-89 of bR is homologous to Ser-l15 of hR from Halobacterium salinarum (shR). X-ray structure of shR has revealed that OH group of this residue directly interacts with CI$\^$-/ Thus, Ser-lI5 of shR is expected to play an important role in CI$\^$-/ binding and transport. In this study, we expressed wild type hR from Natronobacterium pharaonis (PhR) and Sl30A, which corresponds to Ser-l15 of shR, in E. coli in order to clarify binding affinity of chloride ion and photocycle reactions. From the titration with CI$\^$-/, affinity of Sl30A became quite lower than that of WT (WT 6 mM, Sl30A 89 mM). Furthermore, from the flash photolysis with pulse laser of λ$\_$max/ at 532 nm, the reaction rate of SI30A from 0 intermediate to hR ground state was found to become apparently slower than that of WT. The singular value decomposition (SVD) and global fitting analyses of the photocycles were performed to identify all photointermediates and determine the reaction rates.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 1993.05a
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• pp.33-41
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• 1993

The objectives of this experiment performed were to determine the potential using of solar radiation to destroy organic contaminants in water by photolysis and to develop the process and improve its performance. We used lab, scale of recirculation photoreactor with 30, 50, 80ppm initial concentration of TCE and Ti $O_2$ anatase, respectively. Adsorption constant, reaction constant were obtained and compared using the Langmuir-Hinshelwood kinetics equation. Ti $O_2$ anatase demonstrated the highest conversion ratio co TCE among Ti $O_2$ anatase, ZnO and F $e_2$ $O_3$ in this experiment. It was shown that in case of two component system, TCE+ phenol, as the concentration of phenol increased in the feed solution, TCE decomposition rate decreased.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.10
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• pp.927-932
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• 2009

Toxic and recalcitrant organic pollutants in wastewaters can be effectively treated when advanced oxidation and biodegradation are combined, ideally with intimate coupling, in which both processes occur simultaneously in the same system. One means to achieve intimate coupling is to coat nanoscale $TiO_2$ on the outside of macroporous biofilm carriers. This study investigated the kinetics of photocatalysis with $TiO_2$-coated porous carriers. The carriers were made of polyvinyl alcohol (PVA) and coated with $TiO_2$ using a low-temperature sol-gel process. The $TiO_2$-coated carriers catalyzed the oxidation of methylene blue (MB) effectively under irradiation of UV light. The overall reaction rate with adsorption and photolysis saturated at high MB concentration, and approached the adsorption rate, which was first order for all MB concent rations. This result indicates that adsorbed MB may have slowed photocatalysis by blocking active sites for photocatalysis. The overall kinetics could be described by a quasi-Langmuir model. The estimated maximum specific (per unit mass of $TiO_2$) transformation rate of MB by the $TiO_2$-coated carriers was four times larger than that obtained from slurry-$TiO_2$ reactors. This observation demonstrated that the $TiO_2$ present as a coating on the carriers maintained high efficiency for transforming recalcitrant organic matter via photocatalysis. These findings serve as a foundation for advancement of an intimate coupling of photocatalysis to biodegradation.

• Journal of Environmental Science International
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• v.30 no.5
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• pp.413-424
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• 2021

In this study, we quantitatively analyze the effect of ocean emission sources on the simulated O₃ concentrations in South Korea using the community multi-scale air quality (CMAQ) model. To analyze changes in O₃ concentrations by ocean emissions, two different CMAQ simulations considering ocean emissions (OE case) and without considering ocean emissions (NE case) were conducted during the Korea-United States air quality (KORUS-AQ) campaign period (May-June 2016). The changes in the simulated O₃ concentrations due to the effect of ocean emissions (OE case-NE case) appeared mostly in the ocean areas (+1.201 ppbv). The effect of ocean emissions was positive during the daytime (+1.813 ppbv), but negative during the nighttime (-0.612 ppbv). Analysis using the integrated process rate (IPR) confirmed that the increase or decrease in O₃ concentration by ocean emissions was mainly due to chemical processes. Further analysis using the integrated reaction rate (IRR) showed that the daytime increase in O₃ concentration was mainly attributable to the increased O₃ production via O + O₂ + M → O₃ + M reaction as photolysis of NO₂ increased due to the added ocean emissions. The nighttime decrease in O₃ concentration was mainly due to the increased O₃ titration by NO (NO + O₃ → O₂ + NO₂) due to the increased NO emission. These results indicate that the changes in the concentration O₃ in the sea area by the effect of ocean emissions are mainly due to increased NO_x emissions. However, there could be a number of uncertainties in ocean emissions data used in this study, thus continuous comparative research using the most updated data will need to be carried out in the future.

• Journal of Korean Society on Water Environment
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• v.32 no.4
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• pp.357-366
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• 2016

N-nitrosamines are a class of carcinogenic chemicals that can pose significant hazards to the human life. Ultraviolet (UV) light irradiation is considered as one of the effective methods to reduce N-nitrosamines in the aqueous phase. This study aimed to investigate the pH influence on UV photodegradation of N-nitrosamines (i.e., N-nitrosodibutylamine (NDBA) and N-nitrosopyrrolidine (NPYR)) closely related to water treatment. Photodegradation rate constants of NDBA and NPYR remained between 3.26×10^-2 L/W-min to 5.08×10^-3 L/W-min and 1.14×10^-2 L/W-min to 2.80×10^-3 L/W-min at pH2-10, respectively. This study also focused on the formation of oxidized products (i.e., primarily NO^2- and NO^3-). Under slightly acidic and neutral conditions, NO^2- formation was more prevalent than NO^3- formation, while under strong acidic conditions, NO^3- was more prevalent. There was no significant change in total organic carbon (TOC) and total nitrogen (TN), suggesting negligible loss of N-nitrosamines and degradation products from the system. NDBA was easily photodegraded than NPYR. This study also demonstrated that a lower pH is a favorable condition for photolytic degradation of N-nitrosamines in water.