• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.153-160
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• 2005

There have been large areas of soil contaminated with high levels of explosives. For this experimental work, 2,4,6-trinitrotoluene (TNT) was tested as a representative explosive contaminant of concern in both aqueous and soil samples and its removal was evaluated using three different chemical treatment methods: 1) the classical Fenton reaction which utilizes hydrogen peroxide ($H_2O_2$) and soluble iron at pH less than 3; 2) a modified Fenton reaction which utilizes chelating agents, $H_2O_2$, and soluble iron at pH 7; and 3) a Fenton-like process which utilizes iron minerals instead of soluble iron and $H_2O_2$, generating a hydroxyl radical. Using classic Fenton reaction, 93% of TNT was removed in 20 h at pH 3 (soil spiked with 300 mg/L of TNT, 3% $H_2O_2$ and 1mM Fe(III)), whereas 21% removed at pH 7. The modified Fenton reaction, using nitrilotriacetic acid (NTA), oxalate, ethylenediaminetetraacetic acid (EDTA), acetate and citrate as representative chelating agents, was tested with 3% $H_2O_2$ at pH 7 for 24 h. Results showed the TNT removal in the order of NTA, EDTA, oxalate, citrate and acetate, with the removal efficiency of 87%, 71%, 64%, 46%, and 37%, respectively, suggesting NTA as the most effective chelating agent. The Fenton-like reaction was performed with water contaminated with 100 mg/L TNT and soil contaminated with 300 mg/L TNT, respectively, using 3% $H_2O_2$ and such iron minerals as goethite, magnetite, and hematite. In the goethite-water system, 33% of TNT was removed at pH 3 whereas 28% removed at pH 7. In the magnetite-water system, 40% of TNT was removed at pH 3 whereas 36% removed at pH 7. In the hematite-water system, 40% of TNT was removed at pH 3 whereas 34% removed at pH 7. For further experiments combining the modified Fenton reaction with the Fenton-like reaction, NTA, EDTA, and oxalate were selected with the natural iron minerals, magnetite and hematite at pH 7, based on the results from the modified Fenton reaction. As results, in case magnetite was used, 79%, 59%, and 14% of TNT was removed when NTA, oxalate, and EDTA used, respectively, whereas 73%, 25%, and 19% removed in case of hematite, when NTA, oxalate, and EDTA used, respectively.

• Journal of Soil and Groundwater Environment
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• v.14 no.6
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• pp.35-44
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• 2009

Naphthalene and TNT (2,4,6-trinitrotoluene) are defined by U.S. EPA as possible carcinogenic compounds known to have detrimental effects on the aquatic ecosystem and human body. There are, however, few researches on methods of analyzing micro-levels of naphthalene and TNT dissolved in groundwater. This study introduces and evaluates the newly developed analytical methods of measuring naphthalene and TNT in groundwater by using HPLC-FLD (Fluorescence detector) and MSD (Mass detector). The MDL, LOQ and salt effect of these methods, respectively, are compared with those of conventional methods which use HPLC-UV. For the analysis of naphthalene, HPLC-FLD was set in the maxima wavelength (Ex: 270 nM, Em: 330 nM) obtained from 3D-Fluorescence to be compared with HPLC-UV in 266 nM wavelength. The MDL ($0.3\;{\mu}g/L$) and LOQ ($2.0\;{\mu}g/L$) of naphthalene by using HPLC-FLD were approximately 80 times lower than those analyzed by HPLC-UV (MDL: $23.3\;{\mu}g/L$, LOQ: $163.1\;{\mu}g/L$). HPLC-MSD were used in comparison with HPLC-UV in 230 and 254 nM wavelength for the analysis of TNT. The MDL ($0.13\;{\mu}g/L$) and LOQ ($0.88\;{\mu}g/L$) of TNT analyzed by using HPLC-MSD were approximately 130 times lower than those obtained by using HPLC-UV in 230 nM (MDL: $16.8\;{\mu}g/L$, LOQ: $117.5\;{\mu}g/L$). The chromatogram of TNT analyzed by using HPLC-UV in 230 nM displayed elevated baseline as the concentration of ${NO_3}^-$ increases beyond 21 mg/L, while the analysis using HPLC-MSD did not demonstrate any change in baseline in presence of ${NO_3}^-$ of 63.7 mg/L which is 3.5 times higher than average concentration in groundwater. In conclusion, HPLC-FLD and HPLC-MSD may be used as suitable methods for the analysis of naphthalene and TNT in groundwater and drinking water. These methods can be applied to the monitoring of naphthalene and TNT concentration in groundwater or drinking water.

• Journal of Soil and Groundwater Environment
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• v.20 no.6
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• pp.28-36
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• 2015

Simultaneous mobility reduction of explosives and heavy metals in an operational range by monopotassium phosphate (MKP) and bentonite spreading technology was investigated. Potassium ion and phosphate ion in MKP act as explosives sorption enhancer and insoluble heavy metal phosphate formation, respectively, while bentonite acts as the explosives adsorbent. Then, the decrease in surface water concentration of the pollutants and resulting risk reduction for local residents of the operational range, by MKP/bentonite application was estimated. Under untreated scenario, the noncancer hazard index (HI) exceeded unity on February, July and August, mainly due to 2,4,6-trinitrotoluene (TNT); however, MKP/bentonite treatment was expected to lower the noncancer hazard index by decreasing the surface water concentration of explosives and heavy metals (especially TNT). For example, on July, estimated surface water concentration and HI of TNT were 0.01 mg/L and 1.1, respectively, meanwhile the sorption coefficient of TNT was 3.9 mg¹⁻ⁿkg⁻¹Lⁿ. However, by MKP/bentonite treatment, the TNT sorption coefficient increased to 113.8 mg¹⁻ⁿkg⁻¹Lⁿ and the surface water concentration and HI decreased to about 0.002 mg/L and 0.2, respectively. Based on the result, it can be concluded that MKP/bentonite spreading is a benign technology that can mitigate the risk posed by the pollutants migration from operational ranges.

• Journal of Electrochemical Science and Technology
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• v.2 no.2
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• pp.110-115
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• 2011

The effect of $TiO_2$ nanotube (TNT) and nanoparticle (TNP) composite photoelectrode and the role of TNT to enhance the photo conversion efficiency in dye-sensitized solar cell (DSSC) have investigated in this study. Results demonstrated that the increase of the TNT content (1-15 %) into the electron collecting TNP film increases the open-circuit potential ($V_{oc}$) and short circuit current density ($J_{sc}$). Based on the impedance analysis, the increased $V_{oc}$ was attributed to the suppressed recombination between electrode and electrolyte or dye. Photochemical analysis revealed that the increased Jsc with the increased TNT content was due to the scattering effect and the reduced electron diffusion path of TNT. The highest $J_{sc}$ (12.6 mA/$cm^2$), Voc (711 mV) and conversion efficiency (5.9%) were obtained in the composite photoelectrode with 15% TNT. However, $J_{sc}$ and $V_{oc}$ was decreased for the case of 20% TNT, which results from the significant reduction of adsorbed dye amount and the poor attachment of the film on the fluorine-doped tin oxide (FTO). Therefore, application of this composite photoelectrode is expected to be a promising approach to improve the energy conversion efficiency of DSSC.

• Advances in environmental research
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• v.1 no.1
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• pp.1-14
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• 2012

We demonstrated that reductive degradation of 2,4,6-Trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (Royal Demolition Explosive, RDX) can be enhanced by bio-reduced iron-bearing soil minerals (IBSMs) using Shewanella putrefaciens CN32 (CN32). The degradation kinetic rate constant of TNT by bio-reduced magnetite was the highest (0.0039 $h^{-1}$), followed by green rust (0.0022 $h^{-1}$), goethite (0.0017 $h^{-1}$), lepidocrocite (0.0016 $h^{-1}$), and hematite (0.0006 $h^{-1}$). The highest rate constant was obtained by bio-reduced lepidocrocite (0.1811 $h^{-1}$) during RDX degradation, followed by magnetite (0.1700 $h^{-1}$), green rust (0.0757 $h^{-1}$), hematite (0.0495 $h^{-1}$), and goethite (0.0394 $h^{-1}$). Significant increase of Fe(II) was observed during the reductive degradation of TNT and RDX by bio-reduced IBSMs. X-ray diffraction and electron microscope analyses were conducted for identification of degradation mechanism of TNT and RDX in this study. 4-amino-dinitrotoluene were detected as products during TNT degradation, while Hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine, Hexahydro-1,3-dinitroso-5-nitro-1,3,5triazine, and Hexahydro-1,3,5-trinitroso-1,3,5-triazine were observed during RDX degradation.

• Microbiology and Biotechnology Letters
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• v.32 no.3
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• pp.230-237
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• 2004

In this study nitroreductase from Pseudomonas sp. HK-6 capable of degrading 2,4,6-trinitrotoluene (TNT) was characterized. Through a series of purification process including ammonium sulfate precipitation, DEAE-sepharose, and Q-sepharose, three different fractions I, II, and III having the enzyme activity of NTRs whose molecular weights were approximately 27 kDa were detected in fractions from HK-6 cells. Specific activity of the three fractions were approximately 4.85 unit/mg, 5.47 unit/mg, and 5.01 unit/mg, and concentrated to 9.0-, 10.1-, and 9.3-fold compared to crude extract, respectively. The optimal pH and temperature for the three NTR fractions were approximately 7.5 and $30^{\circ}C$, respectively. Metal ions, $Ag^{＋}$ , $Cu^{ 2+}$, $Hg^{2＋}$ inhibited approximately 70% of enzymes activities of all NTR, while $Fe^{2＋}$ did not stimulate or inhibit the activities. Monitoring the effect of chemicals on the enzyme activity revealed that those NTR fractions lost enzyme activity in presence of $\beta$-mercaptoethanol, but were a little influenced by dithiothreitol, EDTA and NaCl. The three NTR fractions demonstrated enzyme activities for nitrobenzene and RDX as well as TNT.

• Explosives and Blasting
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• v.40 no.3
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• pp.44-53
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• 2022

This study evaluates the applicability of the TNT Equivalency Method, Multi-Energy Method, and Baker-Strehlow-Tang (BST) Method, which are blast prediction models used to determine the overpressure of blast wave generated from vapor cloud explosion. It is assumed that the propane leaked from a propane storage container with a capacity of 2000 kg installed in an area where studio houses and shopping centers are concentrated causes a vapor cloud explosion. The equivalent mass of TNT calculated by applying the TNT Equivalency Method is found to be 4061 kg. Change of overpressure with the distance obtained by the TNT Equivalency Method, Multi-Energy Method, and BST Method is rapid and the magnitude of overpressure obtained by the TNT Equivalency Method and BST method is generally similar within 100 m from explosion center. As a result of comparing the overpressure observed in the actual vapor cloud explosion case with the overpressure obtained by applying the TNT Equivalent Method, Multi-Energy Method, and BST Method, the BST Method is found to be the best fit. As a result of comparing the overpressure with the distance obtained by each explosion prediction model with the damage criteria for structure, it is estimated that the structure located within 90 m from explosion center would suffer a damage more than partial destruction, and glass panes of the structure separated by 600 m would be fractured.

• Explosives and Blasting
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• v.34 no.1
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• pp.1-10
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• 2016

On August 12, 2015, two huge explosions were accidently happened in Tianjin port, China. The explosion energies of the two explosions were similar to those of TNT 3 tons and TNT 21 tons. Until now, the cause of the explosions was not clearly announced but some guesses of the cause were released. One of the possible cause of the explosion is the generation of explosive acetylene gas from the chemical reaction between $CaC_2$ and spraying water to extinguish fire happened at the storage site of different chemical compounds. The explosion of acetylene gas might ignite the explosion of 800 tons of ammonium nitrate. In this study, the explosion due to the scenario was analyzed in order to check that such a chemical reaction can produce the huge explosion observed at the Tianjin accident.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.09a
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• pp.102-106
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• 2003

The uptake of $^{14}C$-2, 4, 6-trinitrotoluene (TNT) in hydroponics was studied using onion plants. Of the total TNT mass (5 $\mu\textrm{M}$ concentration), 75% was in the roots, 4.4% in the leaves, and 21% in the external solution at 2 days, The percent distribution in roots was lower with higher concentration in the external solution, but in leaves it was comparable at all concentrations (5-500 $\mu\textrm{M}$). Root concentration factor (RCF) in hydroponics was more than 85 in constant hydroponic experiment (CHE) at 5 $\mu\textrm{M}$ and 150 in non-constant hydroponic experiment (NHE) at 5 $\mu\textrm{M}$. The maximum RCF values in the hydroponic system were greater with lower solution concentration. Transpiration stream concentration factor (TSCF) values in the present study (NHE only: 0.31-0.56) were relatively similar to the values with predicted values (0.43-0.78), increasing with higher external TNT concentration. For phytotoxicity tested in hydroponics and wet paper method, 500 $\mu\textrm{M}$ was toxic to onion plant, 50 $\mu\textrm{M}$ was non-toxic for plant growth but limited the transpiration rate, and 5 $\mu\textrm{M}$ was non-toxic as control.

• Journal of the Korea Institute of Military Science and Technology
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• v.8 no.4 s.23
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• pp.120-129
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• 2005

To analyze a blast effect of developed explosives, three different kinds of aluminized tastable explosives and melted cast explosive TNT were used. Conventional explosive TNT was used as a reference. Each tested explosive charge of 340mm diameter spherical type was initiated at the charge center with DXD-65(${\sim}750g$) booster and RP-87 EBW detonator. Thirteen piezo type pressure sensors were located at a range from 4 to 50m away from the charge. From the blast wave profiles, we calculated a peak blast pressure and impulse of the explosion. The calculated pressures and in pulses were converted to TNT Equivalent Weight(TEW) factor by the scaling ]aw method. The average TEW factors based on the blast pressure of TX-01, TX-02, TX-03, TX-04 were 1.298, 1.05, 1.266, 1.274 and the average TEW factors based on impulse were 1.504, 1.686, 1.640, 1.679. From the results, we concluded that TEW factors based on blast pressure and based on impulse of aluminized explosives were superior to TNT. This results are owing to the high contents of aluminum in formulations.