• Reduction of High Explosives (HMX, RDX, and TNT) Using Micro- and Nano- Size Zero Valent Iron: Comparison of Kinetic Constants and Intermediates Behavior
  • Bae, Bum-Han;
  • Department of Civil & Environmental Engineering, Kyungwon University;
  • 마이크로와 나노 철을 이용한 고성능 화약물질(HMX, RDX 및 TNT)의 환원처리: 중간산물의 거동과 도역학 상수의 비교
  • 배범한;
  • 경원대학교 공과대학 토목환경공학과;
Abstract
Reduction kinetics and the behaviour of intermediate of three high explosives (HMX, RDX, and TNT) were studies in batch reactors using nano- or micro- size zero valent iron(nZVI or mZVI) as reducing agent. The kinetic constants normalized by the mass of iron ($k_M$) or by the surface area ($k_{SA}$) were measured and compared along with the changes in the concentrations of intermediates. Results showed that $k_M$ and $k_{SA}$ values were not suitable to fully explain the behaviour of mother compounds and reduced intermediates in the batch reactor. The concentrations of initial explosives degradation products, such as nitroso-RDXs, nitroso-HMXs, and hydroxylamino-TNTs, were higher in mZVI treated reactor than in nZVI treated reactor, whereas more reduced polar intermediates such as TAT were accumulated in the nZVI reactor. Therefore, a new parameter, which accounted for the intermediates reduction, needs to be developed.

회분식 반응조에서 마이크로(mZVI) 및 나노(nZVI) 크기의 영가 철을 환원물질로 이용하여 고폭화약물질 3종에 대한 환원동역학을 측정하였다. 각 화약류를 이용하여 어미물질에 대한 nZVI와 mZVI의 비표면적 환원상수 $k_{SA}$과 비중량 환원상수 $k_{M}$을 측정한 후, 중간산물의 거동을 비교하였다. 그 결과 두 상수를 사용해서는 nZVI 반응조내 어미 물질과 중간환원산물들의 거동을 완전히 설명할 수 없었다. 화약물질을 mZVI로 처리한 반응조에서는 초기 환원물질인 nitroso-RDXs, nitroso-HMXs 및 hydroxylamino-TNT가 주로 축적되었으나, nZVI로 처리한 반응조에서는 동일한 겉보기 반응속도임에도 불구하고 환원말기물질인 극성중간산물들과 TAT가 축적되었다. 그러므로 중간산물들의 환원까지 고려하는 새로운 매계변수의 개발이 필요한 것으로 판단된다.

Keywords: HMX;RDX;TNT;ZVI;Reduction;Micro vs Nano iron;

Keywords: 0가 철;환원;마이크로와 나노 철;

References
  • 1. 배범한, 1999, 금속 철을 이용한 TNT 환원시의 동역학 산정, 한국토양학회지, 4, 97-108
  •  
  • 2. 한국수자원공사, 다락대 사격장내 토양오염 정밀조사를 통한 한탄강댐 수질예측 및 복원공법 연구 (2002)
  •  
  • 3. 한국수자원공사, 군남홍수조절지 건설사업 사격장 피탄지 토양오염 정밀조사 보고서 (2005)
  •  
  • 4. Bae, B., Nurmi, J.T., and Tratnyek, P.G., Reductive degradation of hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX)with zero valent iron in the presence of electron transfer mediators, Proceedings of Society of Environmental Toxicology and Chemistry Conference, Portland, (2005)
  •  
  • 5. Bandstra, J.Z., Miehr, R., Jonhson, R.L., and Tratnyek, P.G., 2005, Reduction of 2,4,6-trinitrotoluene by iron metal: Kinetic controls on product distribution in batch experiments, Environ. Sci. Technol., 39(1) 230-238
  •  
  • 6. Borch T. and Gerlach, R., 2004, Use of reversed-phase high-performance liquid chromatography-diode array detection for complete separation of 2,4,6-trinitrotoluene Metabolites and EPA method 8330 explosives: Influence of temperature and an ionpair reagent, J. Chromatography A, 1022, 83-94
  •  
  • 7. Devlin, J.F., Klausen, J., and Schwarzenbach, R.P., 1998, Kinetics of nitroaromatic reduction on granular iron in recirculating batch experiments, Environ. Sci. Technol., 32(13), 1941-1947
  •  
  • 8. Dunnivant, F.M., Schwarzenbach, R.P., and Macalady, D.L., 1992, Reduction of substituted nitrobenzenes in aqueous solutions containing natural organic matter, Environ. Sci. Technol., 26(11), 2133-2141
  •  
  • 9. Feng, J. and Lim, T.-T., 2005, Pathways and kinetics of carbon tetrachloride an chloroform reductions by nano-scale Fe and Fe/ Ni particles: comparison with commercial micro-scale Fe and Zn, Chemosphere, 59, 1267-1277
  •  
  • 10. Gregory, K.B., Larese-Casanova, P., Parkin, G.E., and Scherer, M.M., 2004, Abiotic transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine by FeII bound to magnetite, Environ. Sci. Technol., 38(5), 1408-1414
  •  
  • 11. Harderlein, S.B., Weissmahr, K.W., and Schwarzenbach, R. P., 1996, Specific adsorption of nitroaromatic explosives and pesticides to clay minerals, Environ. Sci. Technol., 30(2), 612-622
  •  
  • 12. Jeffrey, I.D. and John, P.K., Human Health Risks from TNT, RDX, and HMX in Environmental Media and Consideration of the U.S. Regularoty Environment, Lawrence Livermore National Laboratory, UCRL-JC-119715 (1994)
  •  
  • 13. Jenkins, T.F., Pennington, J.C., Ranney, T.A., Berry, T.E., Miyares, P.H., Walsh, M.E., Hewitt, A.D., Perron, N.M., Parker, L.V., Hayes, C.A., and Wahlgren, E.G., Characterization of Explosives Contamination at Military Firing Range, Tech Rep. ERDC TR-01-5, USACE Engineering Research and Development Center, Vicksburg, MS (2001)
  •  
  • 14. Klausen J., Trober S.P., Haderlein S.B., and Schwarzenbach, R.P., 1995, Reduction of substituted nitrobenzens by Fe(II) in aqueous mineral suspensions, Environ. Sci. Technol., 29(9), 2396-2404
  •  
  • 15. Lien, H.-L. and Zhang, W.-Z., 2001, Nanoscale iron particles for complete reduction of chlorinated ethenes, Colloids and Surfaces, 191, 97-105
  •  
  • 16. McCormick, M.L. and Adriaens, P., 2004, Carbon tetrachloride transformation on the surface of nanoscale biogenic magnetite particles, Environ. Sci. Technol., 38(4), 1045-1053
  •  
  • 17. Monteil-Rivera, F., Paquet, L., Halasz, A., Montgomery, M.T., and Hawari, J., 2005, Reduction of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine by zero valent iron: Product distribution, Environ. Sci. Technol., 39(24), 9725-9731
  •  
  • 18. Nurmi, J.T., Tratnyek, P.J., Sarathy, V., Baer, D.R., Amonette, J.E., Pecher, K., Wang, C., Linehan, J.C., Matson, D.W., Penn, R.L., and Driessen, M.D., 2005, Characterization and properties of metallic iron nanoparticles: Spectroscopy, electrochemistry, and kinetics, Environ. Sci. Technol., 39(5), 1221-1230
  •  
  • 19. Oh, B.-T., Just, C.L., and Alvarez, P.J., 2001, Hexahydro-1,3,5-trinitro- 1,3,5-triazine mineralization by zerovalent iron and mixed anaerobic cultures, Environ. Sci. Technol., 35(21), 4341-4346
  •  
  • 20. Oh, S.-Y., Cha, D.K., Kim, B.J., and P.C. Chiu, 2002, Effect of adsorption to elemental iron on the transformation of 2,4,6-trinitrotoluene and hexahydro-1,3,5-trinitro-1,3,5-triazine in solution, Environ. Tox. Chem., 21(7) 1384-1389
  •  
  • 21. Ringelberg, D.B., Reynolds, C.M., Walsh, M.E., and Jenkins, T.F., 2003, RDX loss in a suface soil under saturated and well drained conditions, J. Environ., Qual. 32, 1244-1249
  •  
  • 22. Schwarzenbach, R.P., Stierli, R., Lanz, K., and Zeyer, J., 1990, Quinone and iron porphyrin mediated reduction of nitroaromatic compounds in homogeneous aqueous solution, Environ. Sci. Technol., 34(10), 1566-1574
  •  
  • 23. Shermata, T.W., Halasz, A., Paquet, L., Thiboutot, S., Ampleton, G., and Hawari, J., 2001, The fate of cyclic nitramine explosives RDX in nature, Environ. Sci. Technol., 35(6), 1037-1040
  •  
  • 24. Singh, J., Comfort, S.D., and Shea, P.J., 1999, Iron-mediated remediation of RDX-contaminated water and soil under controlled Eh/pH, Environ. Sci. Technol., 33(9), 1488-1494
  •  
  • 25. Spain, J.C., Hughes, J.B., and Knackmuss, H.-J, Biotransformation of Nitroaromatic Compounds and Explosives, Lewis Publishers (2000)
  •  
  • 26. Timothy, L.J., Fish, W., Gorby, Y.A., and Tratnyek, P.G., 1998, Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface, J. of Contam. Hydrol., 29, 379-398
  •  
  • 27. U.S. EPA, Health Advisory for Hexahydor-1,3,5-trinitro-1,3,5- triazine (RDX) Criteria and Standard Division, Office of Drinking Water, Washington, DC (1988)
  •  
  • 28. U.S. EPA, Health Advisory for 2,4,6-trinitrotoluene (TNT) Criteria and Standard Division, Office of Drinking Water, Washington, DC (1988)
  •  
  • 29. Wanaratna, P., Christodoulatos, C., and Sidhoum, M., 2006, Kinetics of RDX degradation by zero-valent iron(ZVI), J. Hazard. Mater., 136(1), 68-74
  •  
  • 30. Wang, C.Y., Zheng, D., and Hughes, J.B., 2000, Stability of hydroxylamino- and amino-intermediates from reduction of 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene, Bitechnol. Lett., 22(1), 15-19
  •  
  • 31. Zhang, B., Kendall, R.J., and Anderson, T.A., 2006, Toxicity of the explosive metabolites hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) and hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) to the earthworm Eisenia fetida, Chemosphere, 64, 86-95
  •  

This Article

  • 2006; 11(6): 83-91

    Published on Dec 31, 2006