Photochemical oxidation of reduced sulfur compounds in an urban location based on short time monitoring data

This study examines the oxidation of reduced sulfur compounds (RSCs) in urban ambient air. The photochemical conversions of RSC (such as DMS, CS₂, H₂S, DMDS, and CH₃SH) to a further oxidized form (e.g., SO₂, MSA, and H₂SO₄) were assessed using a photochemical box model. For our model simulation of RSC oxidation, measurements were taken at an urban monitoring station in Seoul, Korea (37.6° N, 127° E) during three separate time periods (e.g., Sept. 17–18, Oct. 23, and Oct. 27–28, 2003). The results indicate that DMS and H₂S were the dominant RSCs with concentrations of 370 ± 140 and 110 ± 60 pptv, respectively. The photochemical conversion of DMDS to SO₂ was found to occur more efficiently than other RSCs. The overall results of our study suggest that photochemical conversion of RSCs accounted for less than 15% of the observed SO₂ during the measurement period. The SO₂ production from DMS oxidation (mainly by the reaction with OH) was found to be affected primarily by the abstraction channel due to high NO_x levels during the experimental conditions.     

DMS photochemistry during the Asian dust-storm period in the Spring of 2001: model simulations vs. field observations

This study examines the local/regional DMS oxidation chemistry on Jeju Island (33.17 degrees N, 126.10 degrees E) during the Asian dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26, respectively. For comparative purposes, a non-Asian-dust-storm (NADS) period was also considered in this study, which represents the entire measurement periods in April except the ADS events. The atmospheric concentrations of DMS and SO2 were measured at a ground station on Jeju Island, Korea, as part of the ACE-Asia intensive operation. DMS (means of 34-52 pptv) and SO2 (means of 0.96-1.14 ppbv) levels measured during the ADS period were higher than those (mean of 0.45 ppbv) during the NADS period. The enhanced DMS levels during the ADS period were likely due to the increase in DMS flux under reduced oxidant levels (OH and NO3). SO2 levels between the two contrasting periods were affected sensitively by some factors such as air mass origins. The diurnal variation patterns of DMS observed during the two periods were largely different from those seen in the background environment (e.g., the marine boundary layer (MBL)). In contrast to the MBL, the maximum DMS value during the ADS period was seen in the late afternoon at about sunset; this reversed pattern appears to be regulated by certain factors (e.g., enhanced NO3 oxidation). The sea-to-air fluxes of DMS between the ADS and NADS periods were calculated based on the mass-balance photochemical-modeling approach; their results were clearly distinguished with the values of 4.4 and 2.4 micromole m(-2) day(-1), respectively. This study confirmed that the contribution of DMS oxidation to observed SO2 levels on Jeju Island was not significant during our study period regardless of ADS or NADS periods.     

Study on the removal of NOx from simulated flue gas using acidic NaClO2 solution

The study on the removal of NOx from simulated flue gas has been carded out in a lab-scale bubbling reactor using acidic solutions of sodium chlorite. Experiments were performed at various pH values and inlet NO concentrations in the absence or presence of SO2 gas at 45℃. The effect of SO2 on NO oxidation and NO2 absorption was critically examined. The oxidative ability of sodium chlorite was investigated at different pH values and it was found to be a better oxidant at a pH less than 4. In acidic medium, sodium chlorite decomposed into C102 gas, which is believed to participate in NO oxidation as well as in NO2 absorption. A plausible NOx removal mechanism using acidic sodium chlorite solution has been postulated. A maximum NOx removal efficiency of about 81% has been achieved.     

Photochemical oxidation and dispersion of gaseous sulfur compounds from natural and anthropogenic sources around a coastal location

The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H₂S, CH₃SH, DMS, CS₂, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO₂) was produced photochemically during the summer (about 34% of total SO₂ concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO₂ was dominated by H₂S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO₂ concentrations occurred around the D-LF during summer. The total SO₂ concentrations produced from source type N around the D-LF during the summer (a mean SO₂ concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO₂ emissions and their photochemistry along with the wind convergence.     

Characteristics of Asian dust transport based on synoptic meteorological analysis over Korea

Classification of synoptic patterns and their correlation with dust events over East Asia were performed by means of cluster analysis. The average linkage and K-means clustering techniques were used to identify two major weather types during Asian dust events (ADEs; total 26 ADEs with 47 dusty days) of six spring seasons from 1996 to 2001. The first weather type mainly influenced neighboring Asian countries and frequently occurred with ADEs (approximately 23% of ADE cases). It mostly occurred under a surface high (low)-pressure system over the west (east) of the Korean peninsula coupled with an upper-level trough and cutoff low passage over the center of the Korean peninsula. It showed strong advection in the middle/ upper troposphere with both a high aerosol index and enhanced coarse particulate matter (PM) loading over Korea. In contrast, the second weather type was mostly associated with long distance or continental-scale transport and occurred less frequently with ADEs (approximately 15%). It appeared with an upper-level trough and a cutoff low vertically connected with a surface low system that was formed by a strong cyclonic vortex over the north of the Korean peninsula. There were weak advection, low aerosol index, and low coarse PM concentration over the Korean peninsula during the second weather type. In addition, it was found to be mostly associated with the trans-Pacific transport of Asian dust to the western coast of North America.     

Polytitanium sulfate (PTS): Coagulation application and Ti species detection

Interest in the development of inorganic polymerized coagulants is growing; however, there are only limited studies on the synthesis of polytitanium coagulants, which are expected to exhibit improved coagulation efficiency with better floc properties. This study presents the synthesis of polytitanium sulfate (PTS) for potential application in water purification, followed by characterization of PTS flocs and titanium species detection. Stable PTS solutions were successfully synthesized and standard jar tests were conducted to evaluate their coagulation efficiency. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) speciation analysis revealed that a variety of mononuclear and polynuclear complexes were formed in PTS solution, indicating the polymeric nature of the synthesized coagulant. Floc characteristics were studied through on-line monitoring of floc size using a laser diffraction particle size analyzer. Results showed that PTS had a comparable or in some cases even higher organic matter and particulate removal efficiency than Ti(SO₄)₂. The effluent pH after PTS coagulation significantly improved toward desirable values closer to neutral pH. Properties of flocs formed by PTS were significantly improved in terms of floc size, growth rate and structure. This study showed that PTS could be an efficient and promising coagulant for water purification, with the additional benefit that its coagulated sludge can be used to recover valuable TiO₂ nanoparticles for various commercial applications.     

Assessment of the photochemistry of OH and NO3 on Jeju Island during the Asian-dust-storm period in the spring of 2001

In this study, we examined the influence of the long-range transport of dust particles and air pollutants on the photochemistry of OH and NO3 on Jeju Island, Korea (33.17 degrees N, 126.10 degrees E) during the Asian-dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26. Average concentration levels of daytime OH and nighttime NO3 on Jeju Island during the ADS period were estimated to be about 1x10(6) and 2x10(8) moleculescm(-3) ( approximately 9 pptv), respectively. OH levels during the ADS period were lower than those during the non-Asian-dust-storm (NADS) period by a factor of 1.5. This was likely to result from higher CO levels and the significant loading of dust particles, reducing the photolysis frequencies of ozone. Decreases in NO3 levels during the ADS period was likely to be determined mainly by the enhancement of the N2O5 heterogeneous reaction on dust aerosol surfaces. Averaged over 24 h, the reaction between HO2 and NO was the most important source of OH during the study period, followed by ozone photolysis, which contributed more than 95% of the total source. The reactions with CO, NO2, and non-methane hydrocarbons (NMHCs) during the study period were major sinks for OH. The reaction of N2O5 on aerosol surfaces was a more important sink for nighttime NO3 during the ADS due to the significant loading of dust particles. The reaction of NO3 with NMHCs and the gas-phase reaction of N2O5 with water vapor were both significant loss mechanisms during the study period, especially during the NADS. However, dry deposition of these oxidized nitrogen species and a heterogeneous reaction of NO3 were of no importance.     

Characteristics of malodor pollutants and aromatic VOCs around an urban valley in Korea

In this study, the environmental behavior of malodor pollutants (MPs) [including reduced sulfur compounds (RSCs)] and aromatic volatile organic compounds (AVOCs) were investigated around urban valley areas during several field campaigns (February through December 2006). The MPs measured in the study area include the RSCs (H(2)S, CH(3)SH, DMS, and DMDS), ammonia (NH(3)), and styrene (STY); the AVOCs include benzene (BEN), toluene (TOL), ethylbenzene (EB), m,p-xylene (MPX), and o-xylene (OX). The variation of most MP concentrations (except for DMDS) was found to be larger than that of AVOCs. It was found that STY (2,346 +/- 4,867 ppbv) was the most dominant MP followed by NH(3) (447 +/- 285), CH(3)SH (16 +/- 41), and the others (<8). The magnitude of AVOCs was found in the following descending order: TOL (1.4 +/- 2.2 ppbv), EB (1.0 +/- 2.1), MPX (0.9 +/- 2.0), and the others (<0.8). The concentration levels of most MPs on industrial (I) and downwind (D) sites were up to an order of magnitude higher than those at non-industrial (N) and upwind (U) sites. For most AVOCs, the former was ~3 times higher than the latter. For malodor intensity in RSCs, CH(3)SH was the dominant contributor. The concentration difference in target compounds between the sites/periods is likely to be caused by the combined effects such as emission sources, geographical features (e.g., semi-closed topography), and meteorological conditions (e.g., wind directions) in and outside the urban valley.     

Effect of mixing on NO removal in the selective noncatalytic reduction reaction process

The effect of mixing of NH₃ and NO on the selective noncatalytic reduction (SNCR) reaction was investigated using a bench-scale reactor. Three different experimental conditions were compared for the removal of NO in the bulk gas with NH₃, a reducing agent, by means of mixing and contacting. The temperature that gave the highest NO removal efficiency was about 800°C when NH₃ was injected with air or NH₃ was premixed and air was injected. It is suggested that control of mixing of the reducing agent and the injection conditions could be a good way to increase NO removal efficiency as well as to lower the reaction temperature. When NH₃ was injected with air, the NO removal efficiency increased with increasing injected air flow if the initial NO concentration was low, whereas for high NO concentrations, the NO removal efficiency slightly increased up to an injected air flow rate of 100 ml/min. A proposed mixed-flow model can be used as a prediction tool for the NO removal efficiency covering various conditions of the real SNCR process.     

Synthesis and characterisation of potassium polytitanate for photocatalytic degradation of crystal violet

Potassium titanate nanostructures were synthesised by hydrothermal treatment of TiO2 （P25） in KOH and H2O2. As-produced powders were characterised by scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, and nitrogen adsorption-desorption methods. Longitudinally-oriented-wire-like structures with a length up to several micrometres and diameters ranging from 10 to 30 nm were obtained. Larger size fibrous nanowires resulting from the hydrotherrnal treatment showed high affinity in adsorbing crystal violet （CV）, which was mainly due to their high surface area. The photocatalytic bleaching of CV solution revealed that the wires are photoactive under ultraviolet light irradiation. Macroporous nanowires are considered as effective adsorbents of CV, capable of photocatalvtic degradation, and they can be easily separated from the solution by settling.