• Journal of Korean Society of Water and Wastewater
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• v.24 no.6
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• pp.775-788
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• 2010

The decomposition of 2,4,6-trinitrotoluene (TNT) and the mass balance of nitrogen (N) species as products were investigated in a UV/H2O2system by varying pH, concentrations of $H_2O_2$, and $O_2$. All experiments were conducted in a semi-batch system employing a 50 mL reaction vessel and a coil-type quartz-tube reactor. In contrast with previous studies employing batch mode, TNT decomposition in the semi-batch mode was proportionally enhanced by increasing $H_2O_2$ concentration to 10 mM (0.034%), indicatingthat an inhibitory effect of excess $H_2O_2$on hydroxyl radical (${\cdot}OH$) can be negligible. N compounds are released as $NO_2^-$ in the early stages of the reaction, but $NO_2^-$ is rapidly oxidized to $NO_3^-$ by means of ${\cdot}OH$. $NH_4^+$ was also detected in this study and showed gradually the increase with increasing reaction time. In this study, $NH_4^+$ production can involve the reduction of nitro group of TNT concurrent with the production of $NO_3^-$. Of the N species originating from TNT decomposition, 12 ~ 72% were inorganic forms (i.e. [$NO_3^-$] + [$NO_2^-$] + [$NH_4^+$]). This result suggests that the large remaining N portions indicate that unidentified N compounds can exist.

• Journal of Environmental Science International
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• v.16 no.4
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• pp.393-397
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• 2007

The sonolytic decomposition of NHCs(Nitrogen Heterocyclic Compounds), such as atrazine[6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine], simazine(6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine), trietazine(6-chloro-N,N,N'-triethyl-1,3, 5-triazine-2,4-diamine), in water was investigated at a ultrasound frequency of 200kHz with an acoustic intensity of 200W under argon and air atmospheres. The concentration of NHCs decreased with irradiation, indicating pseudo-first-order kinetics. The rates were in the range $1.06{\sim}2.07({\times}10^{-2}min^{-1})$ under air and $1.30{\sim}2.59({\times}10^{-2}min^{-1})$ under argon at a concentration of $200{\mu}M$ of NHCs. The rate of hydroxyl radicals(${\bullet}{OH}$) formation from water is $19.8{\mu}M\;min^{-1}$ under argon and $14.7{\mu}M\;min^{-1}$ under air in the same sonolysis conditions. The sonolysis of NHCs is effectively inhibited, but not completely, by the addition of t-BuOH(2-methyl-2-propanol), which is known to be an efficient ${\bullet}{OH}$ radical scavenger in aqueous sonolysis. This suggests that the main decomposition of NHCs proceeds via reaction with ${\bullet}{OH}$ radical; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fenton's reagent $[Fe^{2+}]$ accelerates the decomposition. This is probably due to the regeneration of ${\bullet}{OH}$ radicals from hydrogen peroxide, which would be formed from recombination of ${\bullet}{OH}$ radicals and which may contribute a little to the decomposition.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2003.11a
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• pp.171-176
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• 2003

The sonolytic decomposition of NHCs, such as atrazine［6-chloro-N-ethyl-N＇ -(1-methylethyl)-1,3,5-triazine-2,4-diamine］, simazine( 6-chloro-N,N＇ -diethyl-l ,3,5-triazine-2,4-diamine), trietazine(6-chloro-N,N,N＇-triethyl-l,3,5-triazine-2,4-diamine), in water was investigated at a ultrasound frequency of 200kHz with an acoustic intensity of 200W under argon and air atmospheres. The concentration of NHCs decreased with irradiation, indicating pseudo-first-order kinetics. The rates were in the range 1.06∼2.07 (x10/sup -3/ min/sup -1/) under air and 1.30∼2.59(x10/sup -3/ min/sup -1/)under argon at a concentration of 200μM of NHCs. The rate of hydroxyl radicals(·OH) formation from water is 19.8μM min/sup -1/ under argon and 14.7 μM min/sup -1/ under air in the same sonolysis conditions. The sonolysis of NHCs is effectively inhibited, but not completely, by the addition of t-BuOH(2-methyl-2-propanol), which is known to be an efficient ·OH radical scavenger in aqueous sonolysis. This suggests that the main decomposition of NHCs proceeds via reaction with ·OH radical; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fenton's reagent ［Fe/sup 2＋/］ accelerates the decomposition. This is probably due to the regeneration of ·OH radicals from hydrogen peroxide, which would be formed from recombination of ·OH radicals and which may contribute a little to the decomposition.

• Journal of Soil and Groundwater Environment
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• v.11 no.6
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• pp.76-82
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• 2006

Fenton's reaction are difficult to apply in the field due to the low pH requirements for the reaction and the loss of reactivity caused by the precipitation of iron (II) at neutral pH. Moreover, Fenton-like reactions using iron mineral instead of injection of iron ion as a catalyst are operated to get high removal result at low pH. Because hydroxyl radical can generate at the surface of iron mineral, there are competition with a lot of hydroxide at around neutral pH. On the other side, to operate Fenton's reaction series at neutral pH, modified Fenton reaction is suggested. The complexes, composed by iron ions (ferrous ion or ferric ion)-chelating agent, could be acted as a catalyst and presented in the solution at neutral pH. However, modified Fenton reaction requires a lot of hydrogen peroxide. Accordingly, the purpose of this experiment was to effectively combine Fenton-like reaction and modified Fenton reaction for extending application of Fenton's reaction. i.e., injecting chelating agents in Fenton-like reaction at around neutral pH is increasing the concentration of dissolved iron ion and highly promoting the oxidation effect. 2,4,6-trinitrotoluene (TNT) was used as a probe compound for comparing reaction efficiencies in this study. If the concentration of dissolved iron ion in combined Fenton process were existed more than 0.1 mM, the total TNT removal were increased. Magnetite-NTA system showed the best TNT removal (76%) and Magnetite-EDTA system indicated about 56% of TNT removal. The results of these experiments proved more promoted 40-60% of TNT removal than Fenton-like reaction's.

• Journal of Korean Society of Water and Wastewater
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• v.31 no.6
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• pp.481-490
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• 2017

Water and wastewater treatment has always been a challenging task due to the continuous increase in amount and the change in characteristics of the poorly biodegradable and highly colored organic matters, as well as harmful micro-organisms. Advanced techniques are therefore required to successfully remove these pollutants from water before reuse or discharge to receiving water bodies. Application of ozone, which is a powerful oxidant and disinfectant, alone or as part of advanced oxidation process depends on the complex kinetic reactions and the mass transfer of ozone involved. Micro- and nano bubbling considerably improves gas dissolution compared to conventional bubbles and hence mass transfer. It can also intensify generation of hydroxyl radical due to collapse of the bubbles, which in turn facilitates oxidation reaction under both alkaline as well as acidic conditions. This review gives the overview of application of micro- and nano bubble ozonation for purification of water and wastewater. The drawbacks of previously considered techniques and the application of the hydrodynamic ozonation to synthetic aqueous solutions and various industrial wastewaters are systematically reviewed.

• Journal of Korean Society on Water Environment
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• v.18 no.2
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• pp.169-187
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• 2002

The effects of important parameters such as reaction time and pH on the Fenton's process were evaluated using a batch reactor. It was proven that organic materials and heavy metals in leachate could be successfully removed by Fenton's reagent. Favorable operation conditions were investigated. It was observed that the reaction between ferrous iron and hydrogen peroxide with the production of hydroxyl radical was almost complete in 10 minutes. That is, the oxidation of organic materials by Fenton's reagent was so fast that it was complete in 30 minutes with batch experiments. With the formation of carbonic acid, pH of the batch reactor decreased to favorable acidic conditions without acid addition. The oxidation of organic materials in the leachate showed a pH dependence and was most efficient in the pH range of 2-3.

• Mass Spectrometry Letters
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• v.8 no.1
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• pp.1-7
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• 2017

Studies performed on heterogeneous reactions of hydroxyl radicals (OH) in aerosol materials of tropospheric interest are presented, focusing on the chemical ionization mass spectrometric approach. Kinetic investigations of these reactions reduced deviation in the estimation of OH concentration in the troposphere by atmospheric modeling from field measurements. Recently, OH uptake was investigated under wet conditions to acquire kinetic information under more realistic conditions representative of the troposphere. The information on the mechanism and kinetics of OH uptake by tropospheric aerosol materials will contribute to the updating of atmospheric models, allowing a better understanding of the troposphere.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2694-2698
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• 2014

A multisegmented polystyrene (PS) with pH-cleavable ester and carbamate linkages was successfully synthesized by a combination of atom transfer radical polymerization (ATRP) and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide and alkynes (click chemistry). ATRP was employed to synthesize polystyrene from hydroxyl-terminated initiator using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) as the catalyst. The reaction of the resulting PS with sodium azide yielded the azido-terminated polymer. The hydroxyl group in the other end of the polymer was reacted with 4-nitrophenyl chloroformate (NPC), followed by reaction with propargylamine to produce an alkyne end group with a carbamate linkage. The PS with an alkyne group in one end and an azide group in the other end was then self-coupled in the presence of CuBr/2,2'-bipyridyl (bpy) in DMF to yield a desired multisegmented PS. Molecular weight and molecular weight distribution of the self-coupled polymer increased with time, as in the typical step-growth-type polymerization processes. Finally, we demonstrated that the ester and carbamate linkages of the multisegmented PS were hydrolyzed in the presence of HCl to yield individual PS chains.

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.171-176
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• 2012

A novel chemiluminescence (CL) system was established for the determination of cytosine arabinoside (Ara-C) in pharmaceutical preparations. It was showed that a clear CL signal was observed when Eosin Y mixed with Fenton reagent. The CL intensity was decreased significantly when Ara-C was added to the reaction system and partially scavenged the hydroxyl radicals in the solution. The extent of decrease in the CL intensity had a good stoichiometrical relationship with the Ara-C concentration. Based on this, we developed a new method for the determination of Ara-C using a flow injection analysis (FIA) technique with CL detection. Under the optimal conditions, the linear range of Ara-C concentration was $6.0{\times}10^{-9}\sim1.0{\times}10^{-7}mol/L$ (R = 0.9982) with a detection limit of $7.6{\times}10^{-10}mol/L$ (S/N=3), the RSD was 5.6% for $6.0{\times}10^{-8}mol/L$ Ara-C (n = 11). The method was successfully applied to the determination of Ara-C in injection samples. The possible chemiluminescence reaction mechanism was discussed.

• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1949-1954
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• 2012

We have developed a novel and eco-friendly synthetic route for the preparation of a two-dimensional layered zinc hydroxide with intercalated nitrate anions. The layered zinc hydroxide nitrate, called 'zinc basic salt', was, in general, successfully synthesized, using an electron beam irradiation technique. The 2-propanol solutions containing hydrated zinc nitrate were directly irradiated with an electron-beam at room temperature, under atmospheric conditions, without stabilizers or base molecules. Under electron beam irradiation, the reactive OH radicals were generated by radiolysis of water molecules in precursor metal salts. After further radiolytic processes, the hydroxyl anions might be formed by the reaction of solvated electrons and the OH radical. Finally, the $Zn_5(OH)_8(NO_3)_2{\cdot}2H_2O$ was precipitated by the reaction of zinc cation and hydroxyl anions. Structure and morphology of obtained compounds were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). The chemical components of the products were determined by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). The thermal behavior of products was studied by thermogravimetric (TG) and differential thermal analysis (DTA).