The Contribution of OH radical and the Effect of Adding Oxidants on the Sonolytic Degradation of 1,4-Dioxane

초음파를 이용한 1,4-Dioxane의 처리에서 OH 라디칼의 기여와 산화제 첨가의 효과

  • Son, Hyun-Seok (Institute of Health & Environment, Seoul National University) ;
  • Choi, Seok-Bong (Center for Nanoscale Science & Engineering, North Dakota State University) ;
  • Khan, Eakalak (Department of Civil & Construction Engineering, North Dakota State University) ;
  • Zoh, Kyung-Duk (Institute of Health & Environment, Seoul National University)
  • Published : 2005.06.30

Abstract

This research investigates the effects of adding oxidants such as $Fe^0$, $Fe^{2+}$, and ${S_2O_8}^{2-}$ in the sonolysis of 1,4-D. Results indicate that the degradation could be divided into two steps (initiation and acceleration) kinetically. The initial portion agreed with zero-order expression, while the second portion could be fitted with pseudo first-order expression. In the presence of ${HCO_3}^-$, as a radical scavenger, the degradations of 1,4-D and TOC were suppressed, indicating that OH radical is an important factor in the sonolysis. The overall degradation efficiency of 79.0% in the sonolysis was achieved within 200 minutes. While $Fe^0$, $Fe^{2+}$, and ${S_2O_8}^{2-}$ were individually combined with sonication, the degradation efficiency of 1,4-D increased 18.6%, 19.1%, and 16.5% after 200 min, respectively. The addition of oxidants not only changed the kinetic model from zero to pseudo first order at initiation step, but also increased the rate constants in the acceleration step. The addition of oxidants in the sonolysis of 1,4-D also improved the mineralization of 1,4-D, however, the effect of adding oxidants on the rate increase was similar regardless of the oxidants.

이 연구는 초음파에 의한 1,4-dioxane(1,4-D)의 제거효율의 증가를 위해 $Fe^0$, $Fe^{2+}$, 그리고 ${S_2O_8}^{2-}$와 같은 산화제의 효과를 조사하였다. 실험의 결과 초음파 반응은 속도론적으로 도입단계와 가속단계의 두 부분으로 구분될 수 있었고, 도입단계는 0차 속도 반응 모델, 가속단계는 유사일차 반응 속도 모델에 부합하였다. OH 라디칼의 scavenger인 ${HCO_3}^-$의 존재 하에 1,4-D와 TOC의 분해속도는 감소하였으며, 이는 OH 라디칼이 초음파 반응에서 중요한 요소이라는 것을 의미한다. 초음파 반응에서 반응시간 200분 동안 79.0%의 1,4-D의 감소된 반면에 $Fe^0$, $Fe^{2+}$, 그리고 ${S_2O_8}^{2-}$가 첨가제로 첨가된 경우는 같은 반응시간 동안 각각 18.6%, 19.1%, 그리고 16.5%의 1,4-D의 제거효율의 증가를 보였다. 또한 첨가제들의 투입으로 도입단계의 반응을 0차 반응에서 유사 일차 반응으로 변화시켰으며, 가속 단계에서의 반응 속도를 증가를 가져 왔다. 또한 초음파 반응에 산화제의 첨가에 의해 1,4-D의 무기화의 정도도 증가되었다. 그러나 첨가되는 산화제의 종류에 관계없이 반응속도의 증가는 별 차이를 보이지 않았다.

Keywords

References

  1. Merck Index. An encyclopedia of chemicals, drugs, and biologicals Budavari, S.
  2. Environ. Sci. Technol. v.34 Elucidation of the 1,4-dioxane decomposition pathway at discrete ultrasonic frequencies Beckett, M.A.;Hua, I.
  3. Environ. Sci. Technol. v.24 Occurrence and fate of organic solvent residues in anoxic groundwater at the gloucester landfill Lesage, S.;Jackson, R.E.;Priddle, M.W.;Riemann, P.G.
  4. proceedings of the 2003 GRA's ninth symposium on groundwater contaminants focused 1,4-dioxane & other solvent stabilizer compounds in the environment GRA's 1,4-dioxane conference profiles national challenge of emerging and unregulated contaminants Tom, M.
  5. Chemical Safety Information from Intergovernmental Orgainzations Home Page
  6. Environ. Eng. Sci. v.20 Occurrence and treatment of l,4-dioxane in aqueous environments Zenker, M.J.;Borden, R.C.;Barlaz, M.A.
  7. Environ. Sci. Technol. v.28 Oxidation and biodegradability enhancement of 1,4-dioxane using hydrogen peroxide and ozone Adams, C.D.;Scanlan, P.A.;Secrist, N.D.
  8. Environ. Sci. Technol. v.32 Mechanism of the degradation of 1,4-dioxane in dilute aqueous solution using the UV/hydrogen peroxide process Stefan, M.I.;Bolton, J.R.
  9. Chemosphere v.35 Light-assisted 1,4-Dioxane degradation Maurino, V.;Calza, P.;Minero, C.;Pelizzetti, E.;Vincernti, M.
  10. J. Photochem. Photobiol., A: Chem. v.108 Photocatalytic degradation of 1,4-dioxane in aqueous solution Hill, R.R.;Jeffs, G.E.;Roberts, D.R.
  11. Ultrason. Sonochem. v.2 Power measurement in sonochemistry Ratoarinoro, C.F.;Wilhelm, A.M.;Berlan, J.;Delmas, H.
  12. Ind. Eng. Chem. Res. v.40 Sonochemistry Environmental Science and Engineering Applications Adewuyi, Y.G.
  13. Water Res. v.37 Enhanced sonochemical decomposition of l,4-dioxane by ferrous iron Beckett, M.A.;Hua, I.
  14. Environ. Sci. Technol. v.35 Sonolytic, photolytic, and photocatalytic decomposition of atrazine in the presence of polyoxometalates Hiskia, A.;Ecke, M.;Troupes, A.;Kokopakis, A.;Hennig, H.;Papaconstantinou, E.
  15. Chem. Eng. Sci. v.49 Modeling of a batch sonochemical reactor Prasad Naidu, D.V.;Rajan, R.;Kumar, R.;Gandhi, K.S.;Arakeri, V.H.;Chandrasekaran, S.
  16. Ultrason. Sonochem. v.4 Ultrasound induced aqueous polycyclic aromatic hydrocarbon reactivity Wheat, P.E.;Tumeo, M.A.
  17. Ind. Eng. Chem. Res. v.41 Sonochemical oxidation of carbon disulfide in aqueous solutions: reaction kinetics and pathway Adewuyi, Y.G.;Appaw. C.
  18. Water Res. v.35 Ultrasonic irradiation of dichlorvos: decomposition mechanism Schramm, J.D.;Hua, I.
  19. Environ. Sci. Technol. v.34 Kinetics and mechanism of the enhanced reductive degradation of nitrobenzene by elemental iron in the presence of ultrasound Hung, H.M.;Ling, F.H.;Hoffmann, M.R.
  20. Environ. Sci. Technol. v.34 Mechanism and kinetics of the OH-radical intervention during fenton oxidation in the presence of a significant amount of radical scavenger(CI) Kiwi, J.;Lopez, A.;Nadtochenko, V.
  21. Chemosphere v.44 Hydroxyl radical scavenging role of chloride and bicarbonate ions in the $H_2O_2$/UV Process Liao, C.H.;Kang, S.F.;Wu, F.A.
  22. J. Am. Chem. Soc. v.93 The oxidation of alcohols by fenton's reagent. The effect of copper ion Walling, C.;Kato, S.
  23. Chemosphere v.55 The role of ferrous ion in Fenton and photo-fenton process for the degradation of phenol Kavitha, V.;Palanivelu, K.
  24. Chemosphere v.55 Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion Liang, C.;Bruell, C.J.;Marley, M.C.;Sperry, K.L.
  25. Environ. Sci. Technol. v.34 Pathways and kinetics of chlorinated ethylene and chlorinated acetylene reaction with Fe(0) particles Arnold, W.A.;Roberts, A.L.
  26. Environ. Sci. Technol. v.35 A continuous system for $Fe^0$ reduction of nitrobenzene in synthetic wastewater Mantha, R.;Taylor K.E.;Biswas, N.;Bewtra, J.K.
  27. Chemosphere v.49 Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) Huang, K.C.;Couttenye, R.A.;Hoag, G.E.
  28. Polymer v.37 Ultrasonically enhanced persulfate oxidation of polyethylene surfaces Price, G.J.;Clifton, A.A.;Keen, F.
  29. Chemosphere v.55 Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple Liang, C.;Bruell, C.J.;Marley, M.C.;Sperry, K.L.