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Photo-decomposition Characteristics of 2,4,6-Trinitrotoluene in a UV/$H_2O_2$ Process  

Kwon, Bum-Gun (서울대학교 공과대학 화학생물공학부)
Choi, Won-Yong (포항공과대학교 환경공학부)
Yoon, Je-Yong (서울대학교 공과대학 화학생물공학부)
Publication Information
Journal of Korean Society of Water and Wastewater / v.24, no.6, 2010 , pp. 775-788 More about this Journal
Abstract
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.
Keywords
TNT; N mass balance; semi-batch mode; hydroxyl radical;
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1 Li, Z. M., Shea, P. J. and Comfort, S. D. (1998) Nitrotoluene destruction by UV-catalyzed Fenton oxidation, Chemosphere, 36, pp. 1849-1865.   DOI   ScienceOn
2 Hwang, S., Bouwer, E. J., Larson, S. L. and Davis J. L. (2004) Decolorilation of alkaline TNT hydrolysis effluents using UV/$H_2O_2$, J. Hazard. Mater., 2004, pp. 61-67.
3 Felt, D. R., Larson, S. L. and Valente, E. J. (2002) UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction, Chemosphere, 49, pp. 287-295.   DOI   ScienceOn
4 Fox, M.A. (1983) Organic heterogeneous photocatalysis: Chemical conversions sensitized by irradiation semiconductors, Accounts Chem. Res., 16, pp. 314-321.   DOI
5 Godejohann, M., AStratov, M.,. Preiss, A. and Levsen, K. (1998) Application of continuous-flow HPLC-proton-nuclear magnetic resonance spectroscopy and HPLC-thermospra-mass spectroscopy for the structural elucidation of phototransformation products of 2,4,6-trinitrotoluene, Anal. Chem., 70, pp. 4104-4110.   DOI   ScienceOn
6 Chow, Y. L. (1982) Photochemistry of Nitro and Nitroso compounds. In the chemistry of amino, nitroso and nitro compounds and their derivatives, Part 1, pp. 181-290, J. Wiley, New York.
7 Dillert, R., Fornefett, I., Siebers, U. and Bahnemann, D. J. (1996) Photocatalytic degradation of trinitrotoluene and trinitrobenzene: Influenece of hydrogen peroxide, J. Photochem. Photobiol. A, 94, pp. 231-236.   DOI   ScienceOn
8 Felt, D. R., Larson, S. L. and Hansen, L. D. (2001b) Molecular weight distribution of the final products of TNT-hydroxide reaction (ERDC/EL TR-01-16), U.S. Army Engineer Research and Development Center, Vicksburg, MS.
9 Errunrich, M. (1999) Kinetics of the alkaline hydrolysis of 2,4,6-trinitrotoluene in aqueous solution and highly contaminated soils, Environ. Sci. Technol., 33, pp. 3802-3805.   DOI   ScienceOn
10 Felt, D. R., Larson, S. L. and Hansen, L. D. (2001a) Kinetics of base-catalyzed 2,4,6-trinitrotoluene transformation (ERDC/EL TR-01-17), U.S. Army Engineer Research and Development Center, Vicksburg, MS.
11 Bruns-Nagel, D., Scheffer, S., Casper, B., Garn, H., Drzyzga, O., Von L w, E. and Gemsa, D. (1999) Effect of 2, 4, 6-trinitrotoluene and its metabolites on human monocytes, Environ. Sci. Technol., 33, pp. 2566-2570.   DOI   ScienceOn
12 Buxton, G. V., Greenstock, C. L., Helman, W. P. and Ross, A. B. (1988) In critical review of rate constants for reactions of hydrated electron. hydrogen atoms and hydroxyl radicals $OH/O^-$ in aqueous solution, J. Phys. Chem. Ref. Data, 17.
13 Blake, D. M., Wolfrun, E., Boulter, J., Prairie, M., Showalter, S., Rodacy, P., Leslie, P. and Stange, B. (1996) Photocatalytic oxidation and reduction chemistry and a new process for treatment of pink water and related contaminated water (Rep. No. NREL/TP-430-21580), National Renewable Energy Laboratory (NREL), Golden, CO.
14 Chen, W-S and Liang, J-S. (2008) Decomposition of nitrotoluenes from trinitrotoluene manufacturing process by electro-Fenton oxidation, Chemosphere, 72, 601-607.   DOI   ScienceOn
15 Chen, W-S and Lin, S-Z. (2009) Desctruction of nitrotoluenes in wastewater by electro-Fenton oxidation, Journal of Hazardous Materials, 168, 1562-1568.   DOI   ScienceOn
16 Alnaizy, R. and Akgerman, A. (1999) Oxidative treatment of high explosives contaminated wastewater, Water Res., 33, pp. 2021-2030.   DOI   ScienceOn
17 Andrews, C. C. (1980) Photooxidative treatment of TNT contaminated wastewater (Rep. No. WQEC/C-80-137: AD-AQ84684), Weapons Quality Engineering Center, Naval Weapons Support Center, Crane, Ind.
18 Bielski, B.HJ., Cabelli, D. E., Arudi, R. L and Ross, A. B. (1985) Reactivity of $HO_2/O_{2}^-$ radicals in aqueous solution. J. Phys. Chem. Ref. Data, 14, pp. 1041-1051.   DOI
19 Won, W.D., Disalvo, L.B. and James, N.G. (1976) Toxicity and mutagenicity of 2,4,6-trinitrotoluene and its microbial metabolites, Appl. Environ. Microbiol., 31, pp. 576-580.
20 Wang, Z. and Kutal, C. (1995) Photocatalytic mineralization of 2,4,6-trinitrotoluene in aqueous suspension of titanium dioxide, Chemosphere, 30, pp. 1125-1136.   DOI   ScienceOn
21 Zafiriou, O. C. and Bonneau, R. (1987) Wavelength-dependent Quantum yield of OH radical formation from photolysis of nitrite ion in water, Photochem. Photobiol., 45, pp. 723-727.   DOI   ScienceOn
22 Schmelling, D. C. and Gray, K. A. (1995) Photocatalytic transformation and mineralization of 2,4,6-trinitrotoluene (TNT) in $TiO_2$ slurries, Water Res., 29, pp. 2651-2662.   DOI   ScienceOn
23 US Agency for Toxic Substances and Disease Registery (ATSDR), Toxicological Profile for 2,4,6-Trinitrotoluene, http://www.atsdr.cdc.gov/ (1995).
24 Nahen, M., Bahnemann, D., Dillert, R. and Fels, G. J. (1997) Photocatalytic degradation of trinitrotoluene: Reductive and oxidative pathways, J. Photochem. Photobiol. A, 110, pp. 191-199.   DOI   ScienceOn
25 Noss, C. I. and Chyrek, R. H.(1984) Tertiary treatment of effluent from holston AAP industrial liquid waste treatment facility IV. Ultraviolet radiation and hydrogen peroxide studies: TNT, RDX, HMX, TAX, and SEX (Rep. No. 8308: AD-A141 135), US Army Medical Research and Development Command, Frederick, MD.
26 Pennington, J.C. and Brannon, J.M. (2002) Environmental fate of explosives, Thermochim. Acta, 384, pp. 163-172.   DOI
27 Rodgers, J. D. and Bunce, N. J. (2001) Treatment methods for the remediation of nitroaromatic explosives, Water Res., 35, pp. 2101-2111.   DOI   ScienceOn
28 Mahdavi, F., Bruton, T. C. and Li, Y. (1993) Photoinduced reduction of nitro compounds on semiconductor panicle, J. Org. Chem., 58, pp. 744-746.   DOI
29 Low, G. K.-C., McEvoy, S. R. and Matthews, R. W. (1991) Formation of nitrate and ammonium ions in titanium dioxide mediated photocatalytic degradation of organic compounds containing nitrogen atoms, Environ. Sci. Technol., 25, pp. 460-467.   DOI
30 Lynch, J. C., Myers, K. F., Brannon, J. M. and Delfino, J. J. (2001) Effects of pH and Temperature on the aqueous solubility and dissolution rate of 2,4,6-trinitrotoluene (TNT), Hexahydro-1,3,5-trinitro-1,3,5-triazine-tetrazocine (RDX), and Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), J. Chem. Eng. Data, 46, 1549-1555.   DOI   ScienceOn
31 Matta, R. Hanna, K., Kone, T. and Chiron, S. (2008) Oxidation of 2,4,6-trinitrotoluene in the presence of different iron-bearing minerals at neutral pH, Chem. Eng. J., 144, pp. 453-458.   DOI   ScienceOn
32 Lee, B. and Jeong, S-W. (2008) Effects of additives on 2,4,6-trinitrotoluene (TNT) removal and its mineralization in aqueous solution by gamma irradiation, J. Hazard. Mater., 165, pp. 435-440.
33 Jolas, J.L., Pehkonen, S.O. and Maloney, S.W. (2000) Reduction of 2,4-dinitrotoluene with graphite and titanium mesh cathodes, Water Environ. Res., 72, pp. 179-188.   DOI   ScienceOn
34 Kwon, B. G. and Lee, J. H. (2004) A kinetic method for $HO_2{\cdot}/O_2^-$ determination in advanced oxidation processes, Anal. Chem., 76, pp. 6359-6364.   DOI   ScienceOn
35 Lang, P. S., Ching, W. K., Willberg, D. M. and Hoffmann, M. R. (1998) Oxidative degradation of 2,4,6-trinitroluene by ozone in an electrohydraulic discharge reactor, Environ. Sci. Technol., 32, pp. 3142-3148.   DOI   ScienceOn
36 Hori, Y., Bandoh, A. and Nakatsu, A. (1999) Electrochemical investigation of photocatalytic oxidation of $NO_2^-$ at $TiO_2$ (Anatase) in the presence of $O_2$, J. Electrochem. Soc., 137, pp. 1155-1161.
37 Lenke, H., Warrelmann, J., Daun, G., Hund, K., Sieglen, U., Walter, U. and Knackmuss, H-J. (1998) Biological treatment of TNT-contaminated soil. 2. Biological induced imunobilization of the contaminants and full-scale application, Environ. Sci. Technol., 32, pp. 1964-1971.   DOI   ScienceOn
38 Li, Z. M., Comfort, S. D. and Shea, P. J. (1997) Destruction of 2,4,6-trinitrotoluene by Fenton oxidation, J. Environ. Qual., 26, pp. 480-487.
39 Hawari, J., Halasz, A., Paquet, L., Zhou, E., Spencer, B., Ampleman, G. and Thiboutot, S. (1998) Characterization of metabolites in the biotransformation of 2,4,6-trinitrotoluene with anaerobic sludge: Role of triaminotoluene, Appl. Environ. Microbiol., 64, pp. 2200-2206.