• Asian Journal of Atmospheric Environment
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• v.6 no.4
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• pp.288-303
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• 2012

In this study, real time measurements of particle number size distribution in urban Gwangju, coastal Taean, and industrial Yeosu in Korea were conducted in 2008 to understand the occurrence of ultrafine particle (UFP) (<100 nm) events, the variation of its concentration among different sampling sites, and UFP formation pathways. Also, to investigate seasonal and long-term variation of the UFP number concentration, data were collected for the period of 5 years (2007, 2008, 2010, 2011, and 2012) in urban Gwangju. Photochemical and combustion events were found to be responsible for the formation of UFP in the urban Gwangju site, whereas only photochemical event led to the formation of UFP in the coastal Taean site. The highest UFP concentration was found in industrial Yeosu (the average UFP number fractions were 79, 59 and 58% in Yeosu, Gwangju, and Taean, respectively), suggesting that high amount of gas pollutants (e.g., $NO_2$, $SO_2$, and volatile organic carbon (VOC)) emitted from industries and their photochemical reaction contributed for the elevated UFP concentration in the industrial Yeosu site. The UFP fraction also showed a seasonal variation with the peak value in spring (61.5, 54.5, 50.5, and 40.7% in spring, fall, summer, and winter, respectively) at urban Gwangju. Annual average UFP number concentrations in urban Gwangju were $5.53{\times}10^3\;cm^{-3}$, $4.68{\times}10^3\;cm^{-3}$, $5.32{\times}10^3\;cm^{-3}$, $3.99{\times}10^3\;cm^{-3}$, and $2.16{\times}10^3\;cm^{-3}$ in the year 2007, 2008, 2010, 2011, and 2012, respectively. Comparison of the annual average UFP number concentration with urban sites in other countries showed that the UFP concentrations of the Korean sites were lower than those in other urban cities, probably due to lower source strength in the current site. TEM/EDS analysis for the size-selected UFPs showed that the UFPs were classified into various types having different chemical species. Carbonaceous particles were observed in both combustion (soot and organics) and photochemical events (sulfate and organics). In the photochemical event, an internal mixture of organic species and ammonium sulfate/bisulfate was identified. Also, internal mixtures of aged Na-rich and organic species, aged Ca-rich particles, and doughnut shaped K-containing particles with elemental composition of a strong C with minor O, S, and K-likely to be originated from biomass burning nearby agricultural area, were observed. In addition, fly ash particles were also observed in the combustion event, not in the photochemical event.

• Bulletin of the Korean Chemical Society
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• v.26 no.5
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• pp.791-794
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• 2005

A visible photochemistry of maleic to fumaric acid adsorbed on silver nanoparticle surfaces was investigated as probed by SERS using a simple flow method. Photoisomerization of maleic to fumaric acid was consecutively observed in the condition of various flow rates, which varied the exposure time of laser beam. The sequential SERS spectra of maleic acid indicated that the photochemical isomerization and desorption took place simultaneously on silver nanoparticle surfaces as a function of laser fluency and wavelength. For 530.9nm laser line excitation, the rate constant coefficients were obtained with a = 5.9 $sec^{-1}$ mW for isomerization and b = 13.9 $sec^{-1}$ mW for desorption, which $k_1\;=\;aI^n\;and\;k_2\;=\;bI^m$. Both reactions were one photon process (n = 1, m = 1) of a visible light and relatively fast process whose decay time was in the range of milli-second for 50 mW laser power. The rate of photochemical reaction increased on going toward the blue and photodesorption was a dominant process. A simple flow method used in this study was very useful to study a relatively fast photochemical reaction of molecules adsorbed on silver nanoparticle surfaces.

• Journal of Korean Society for Atmospheric Environment
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• v.26 no.2
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• pp.161-176
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• 2010

We examined high ozone episodes observed during the intensive measurement periods (11 May~21 June and 30 July~11 August 2009) in the Gulf of Gwangyang. During that period, there were a few events (or days) in which 1 hr averaged ozone concentrations were greater than 100 ppbv. The analysis of ozone budget and photochemical characteristics related to the ozone production was carried out using a photochemical box model. Ozone sensitivity to $NO_x$ and VOCs was also examined in the study area during the measurement period. Diurnal variation of ozone during the episodes was similar to that of odd hydrogen radicals ($HO_2,CH_3O_2$, and $RO_2$), suggesting significant correlation with photochemical production of ozone during the episodes. In general, ozone concentration in the study area during the measurement period was sensitive to VOCs, whereas ozone was sensitive to $NO_x$ under certain conditions. Ozone sensitivity assessment using a radical budget analysis and $NO_x$/VOCs-control strategy was consistent with that using indicator species ($H_2O_2/HNO_3$ ratio).

• Journal of Korean Society for Atmospheric Environment
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• v.29 no.4
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• pp.390-406
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• 2013

In Korea, photochemical air pollution has drawn public attention as one of the major environmental issues since 1990s. To abate ozone and air pollution, new legislation was enacted and regulation was reinforced in conjunction with basic researches. As a result, the air quality has been much improved in terms of primary pollutant such as CO and the occurrence of extremely high ozone concentration. In Seoul, on the other hand, concentrations of ozone and exeedance hours of its national standard have increased since 2005, which is intimately coupled with $NO_2$ variations. It indicates the need for further research at long-term bases to improve our understanding on complex processes determining ozone concentrations. In this paper, the characteristics of ozone variation was analyzed with 13-year measurement data obtained in Seoul. In addition, the previous studies and their main results were summarized that have been performed in association with photochemical air pollution in Korea over the last three decades.

• Journal of Environmental Impact Assessment
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• v.14 no.3
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• pp.117-126
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• 2005

This study was executed to know the best matrix of photochemical ozone reduction in the metropolitan area. For this object, we used the OZIPR(Ozone Isopleth Plotting Package for Research) model for comparing the effectiveness of VOCs and NOx amount variation about the ozone creation. Among the various ozone reduction scenarios, 50% reduction of VOCs from organic solvent and road traffic respectively was the best matrix for ozone reduction. Although it needs more accurate assessment and confirmation of VOCs and NOx emission amount data, according to existing data, the control of VOCs is the best way for photochemical ozone reduction in Seoul.

• Journal of Korean Society for Atmospheric Environment
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• v.15 no.E
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• pp.55-64
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• 1999

The CIT(California Institute of Technology) three-dimensional Eulerian photochemical model was applied to the Greater Seoul Area, Korea for July 24, 1994, a day of the 9-day ozone episode to understand the characteristics of photochemical air pollution problems in the area. The modeling domain was 60km$\times$60km with the girl size of 2km$\times$2km. As the base case emissions, air pollutant emission data of the National Institute of Environmental Research, Korea for the year of 1991 were used with modifications based on EKMA(Empirical Kinetic Modeling Approach) resutls. Comparisons between predicted and observed concentrations showed that the model predicted the peak concentration over the domain reasonably. It was found that the location of the peak ozone concentration was mainly decided by metorological conditions. But the model could not resolve the spatial variations of concentration station by station, which was mainly caused by localized variations in emission and meteorology.

• Particle and aerosol research
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• v.10 no.1
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• pp.9-17
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• 2014

Several studies have been carried out on the source contribution of the particulate Polycyclic Aromatic Hydrocarbons (PAHs) over Seoul by using the Chemical Mass Balance Model (CMB)(Lee and Kim, 2007; Kim et al., 2013). To confirm the validity of the modeling results, the modified model employing a photochemical loss rate along with varying residence times and the standard model that considers no loss were compared. It was found that by considering the photochemical loss rate, a better performance was obtained as compared to those obtained from the standard model in the CMB calculation. The modified model estimated higher contributions from coke oven, transportation, and biomass burning by 4 to 8%. However, the order of the relative importance of major sources was not changed, coke oven followed by transportation and biomass burning. Thus, it was concluded that the standard CMB model results are reliable for identifying the relative importance of major sources.

• Journal of Environmental Science International
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• v.17 no.10
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• pp.1169-1182
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• 2008

The chemical and meteorological effects on the concentration variations of air pollutants ($O_3$ and its precursors) were evaluated based on ground observation data in coastal and inland regions, Busan during springs and summers of 2005-2006. For the purpose of this study, study areas were classified into 5 categories: coastal area (CA), industrial area (IA), downtown area (DA), residential area (RA), and suburban area (SA). Two sites of Dongsam (DS) and Yeonsan (YS) were selected for the comparison purpose between the coastal and inland regions. $O_3$ concentrations in CA and SA were observed to be highest during spring (e.g., 40 ppb), whereas those in DA and RA were relatively low during summer (e.g., $22\sim24$ ppb). It was found that $O_3$ concentrations in IA were not significantly high although high VOCs (especially toluene of about 40 ppb) and $NO_x$ ($\geq$ 35 ppb) were observed. On the other hand, the concentration levels of $O_3$ and $PM_{10}$ at the DS site were significantly higher than those at the YS site, but $NO_x$ was slightly lower than that at the YS site. This might be caused by the photochemical activity and meteorological conditions (e.g., sea-land breeze and atmospheric stagnance). When maximum $O_3$ (an index of photochemical activity) exceeds 100 ppb, the contribution of secondary $PM_{10}\;((PM_{10})_{SEC})$ to total observed $PM_{10}$ concentrations was estimated up to 32% and 17% at the DS and YS sites, respectively. In addition, the diurnal variations of $(PM_{10})_{SEC}$ at the DS site were similar to those of $O_3$ regardless of season, which suggests that they are mostly secondary $PM_{10}$ produced from photochemical reactions.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1229-1258
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• 2002

This paper reports the photochemical reduction of benzil 1 to benzoin 2 and the reduction of 2 to hydrobenzoin 4 in deoxygenated solvents in the presence of triethylamine (TEA) and/or TiO2. Without TEA or TiO2, the photolysis of 1 resulted in very low yield of 2. The presence of TEA or TiO2 increased the rate of disappearance of 1 and the yield of 2, which were further increased considerably by the presence of water. The photoreduction of 1 to 2 proceeds through an electron transfer to 1 from TEA or hole-scavenged excited TiO2 followed by protonation. In the reaction medium of 88 : 7 : 2 : 3 CH3CN/CH3OH/H2O/TEA with 2.5 $㎎/m{\ell}$ of TiO2, the yield of 2 was as high as 85 % at 50 % conversion of 1. The photolysis of 2 in homogeneous media resulted in photo-cleavage to benzoyl and hydroxybenzyl radicals, which are mostly converted to benzaldehyde. The reduction product 4 is formed in low yield through the dimerization of hydroxybenzyl radicals. The addition of TEA increased the conversion rate of 2 and the yield of 4 significantly. This was attributed to the scavenging effect of TEA for benzoyl radical to produce N,N-diethylbenzamide and the photoreduction of benzaldehyde in the presence of TEA. The ratio of $(\pm)$ and meso isomers of 4 obtained from the photochemical reaction is about 1.1. This ratio is the same as that from the photochemical reduction of benzaldehyde in the presence of TEA. In the TiO2-sensitized photochemical reduction of 2, meso-4 was obtained in moderate yield. The reduction of 2 to 4 proceeds through two consecutive electron/proton transfer processes on the surface of the photocatalyst without involvement of ${\alpha}-cleavage$. The radical 11 initially formed from 2 by one electron/proton process can also combine with hydroxy methyl radical, which is generated after hole trapping of excited TiO2 by methanol, to produce 1,2-diphenylpropenone after dehydration reaction.

• Particle and aerosol research
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• v.9 no.3
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• pp.149-161
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• 2013

Experiments on photochemical reactions of purified air alone in an indoor smog chamber were carried out after flushing Teflon bags with purified air for many hours in order to check the level of contamination on the chamber wall. Ozone concentrations were linearly increased from <4 ppb up to about 8 ppb with irradiation time for four hours. Outgassing of NOx from the chamber wall was found to be less than 1 ppb. New ultrafine particles were formed and grown up to about 70 nm during the photochemical reactions, and then total number and mass concentrations of particles were increased from <10 particles/$cm^3$ up to about 4,000 particles/$cm^3$ and $1.3{\mu}g/m^3$, respectively. The wall conditions of these Teflon bags flushed with purified air might not severly affect the chamber experimental results for photochemical reactions of polluted urban ambient air. The difference of gaseous species between two chambers was 2.4 ppb of ozone at most, indicating that the wall cleaning performance of two chambers was nearly similar.