Photo- and Sonic Degradation of Endosulfans(α, β, and sulfate) in Aqueous Solution

엔도설판류의 광 및 초음파분해

  • Kwon, Sung Hyun (Department of Marine Environmental Engineering, Inst. of Marine Industry, Gyeongsang National University) ;
  • Kim, Jong Hyang (Public Health & Environmental Research Institute at Gyeongnam) ;
  • Cho, Daechul (Department of Energy & Environmental Engineering, Soonchunhyang University)
  • 권성현 (경상대학교 해양과학대학 해양환경공학과(해양산업연구소)) ;
  • 김종향 (경상남도보건환경연구원) ;
  • 조대철 (순천향대학교 에너지환경공학과)
  • Received : 2007.06.07
  • Accepted : 2007.06.29
  • Published : 2007.10.31

Abstract

Endosulfan-${\alpha}$ endosulfan-${\beta}$ and endosulfan-sulfate, which are classified as pesticides, were degraded by use of UV energy and ultrasonic irradiation. The degradation residuals were analysed by gas chromatography with an electron capture detector and TOC (total oragnic carbon) analysis. The reactions were conducted in a quartz annular reactor equipped with a low pressure mercury multilamp (8Wx2) and a sonic generator. All the aqueous solutions were concentrated as 10 mg/L initially. Endosulfans were degraded each to result in 48.2% (${\alpha}$), 50.0% (${\beta}$) and 76.5% (sulfate) of removal efficiency by UV energy, and 66.9% (${\alpha}$), 55.8% (${\beta}$) and 72.7% (sulfate) by ultrasonic irradiation, respectively. In contrast to the results of the single-component solutions, degradation of the endosulfan-sulfate was greatly suppressed to result in the lowest degradation rate and removal efficiency in the three-component solutions. This finding suggests that there should be a reversible reaction with a substantially low equilibrium constant between endosulfan-${\alpha}$ or -${\beta}$ and -sulfate in the coexistence of the three endosulfans. TOC data showed the endosulfans were decomposed by 20%~40% toward complete mineralization, producing a quantity of intermediates induced by the radical reactions. We found that all the decay reactions considered in this study nicely fell into pseudo first-order rate.

엔도설판류(${\alpha}$, ${\beta}$, sulfate)를 UV 및 초음파에너지를 조사하여 분해하였다. 물질의 분해과정은 가스크로마토그래프(GC)와 총유기탄소(TOC)를 분석하여 검토되었다. UV 원으로서 low pressure mercury multilamp(8Wx2)와 초음파발생기를 이용하였으며, 초기농도는 10 mg/L로 하였다. 단일성분에서의 실험결과 엔도설판류(${\alpha}$, ${\beta}$, sulfate)의 UV 광분해도는 순서대로 48.2%, 50.0%, 76.5%였으며, 초음파를 이용한 분해에서는 각각 66.9%, 55.8%, 72.7%였다. 3성분 혼합용액에서는 단일성분용액의 분해효율과 달리 엔도설판-sulfate의 분해속도가 급감하여 가장 낮았고 엔도설판 -${\alpha}$, -${\beta}$들은 두드러진 차이를 보이지 않았다. 혼합용액에서 엔도설판-sulfate의 분해속도 감소로부터 엔도설판-${\alpha}$, -${\beta}$와 엔도설판-sulfate 사이의 낮은 평형상수값을 갖는 가역적 반응을 가정할 수 있었다. TOC 분석자료는 엔도설판류의 무기질화가 약 20%~40% 수준으로 진행되었음을 보여주며, 동시에 두 고도처리법이 라디칼분해반응을 유도하면서 상당한 분율의 중간산물을 생성함을 추정할 수 있었다. 또한 엔도설판류의 분해는 유기물 및 TOC 분석자료에 의거하면 모두 겉보기 1차 속도식과 잘 부합되었다.

Keywords

References

  1. Jeon, M. H. and Choi, S. I., 'Effect of In-Situ Flushing on the Bioremediation of Soil Contaminated with Endosulfan,' J. KOSSGE, 6(2), 39-47(2001)
  2. Kim, J. H., 'Removal and Decomposition of Organochlorine Compounds in Water Using UV Irradiation,' J. Kor. Ind. & Eng. Chem., 10(1), 30-34(1998)
  3. Kam, S. K., Kim, J. Y., Ju, C. S. and Lee, M. G., 'Photodegardation of Pyrene, Chrysene and Benzo[a]pyrene in Water(II),' J. Environ. Sci., 12(7), 775-782 (2003)
  4. Miller, J. and Olejnik, D., 'Photolysis of Polycyclic Aromatic Hydrocarbons in Water,' Wat. Res., 35(1), 233-243(2001) https://doi.org/10.1016/S0043-1354(00)00230-X
  5. Psillakis, E., Goula, G., Kalogerakis, N. and Mantzavinos, D., 'Degradation of Polycyclic Aromatic Hydrocarbons in Aqueous Solution by Ultrasonic Irradiation,' J. Hazard. Mat. B108(2), 95-102 (2004)
  6. Harada, K., Hisanaga, T. and Tanaka, K., 'Photocatalytic Degradation of Organophosphorous Insecticides in Aqueous Semiconductor Suspensions,' Wat. Res., 24(11), 1415-1417(1990) https://doi.org/10.1016/0043-1354(90)90162-Y
  7. Legrini, O., Oliveros, E. and Braun, A. M., 'Photochemical Processes for Water Treatment,' Chem. Rev., 93(2), 671-698(1993) https://doi.org/10.1021/cr00018a003
  8. Choy, W. K. and Chu, W., 'The Modelling of Trichloroethene Photodegradation in Brij 35 Surfactant by Two-stage Reaction,' Chemospere, 44(2), 211-215(2001) https://doi.org/10.1016/S0045-6535(00)00188-0
  9. Bunce, N. J., Diodato, G. D. and Safe, S. H., 'Photolysis of Nitropolychlorodibenzo-p-dioxins with Base as Potential Met odology for the Destruction of Polychlorinated Dibenzo-p-dioxins,' Chemosphere, 24(4), 433-439(1992) https://doi.org/10.1016/0045-6535(92)90418-Q
  10. Addision, J. and Cote, K. A., 'Structure Photodegradation of 4-Thiomethyl-N-Methylphenyl Carbamate,' Chemosphere, 24(2), 181-188(1992) https://doi.org/10.1016/0045-6535(92)90391-4
  11. Min, B. C., Kim, J. H. and Kim, B. K., 'Degradation of Aromatic Pollutants by UV Irradiation,' J. Kor. Ind & Eng. Chem., 8(3), 502-509(1997)
  12. Kawaguchi, H., 'Photooxidation of Phenol in Aqueous Solution in the Presence of Hydrogen Peroxide,' Chemosphere, 24(12), 1707-1712(1992) https://doi.org/10.1016/0045-6535(92)90225-G
  13. Little, C., Hepher, M. J. and El-Sharif, M., 'The Sono-degradation of Phenanthrene in an Aqueous Environment,' Ultrasonics, 40(8), 667-674(2002) https://doi.org/10.1016/S0041-624X(02)00196-8
  14. Kwon, S.-H., Kim, J. H. and Cho, D., 'Degradation of PAHs in Aqueous Solution by UV Energy and Ultrasonic Irradiation,' J. Environ. Sci., 15(7), 669-676(2006) https://doi.org/10.5322/JES.2006.15.7.669
  15. Kim, J. H. and Lee, M. H., 'Removal and Photodecomposition of Haloacetonitriles of Disinfection by products,' J. KSSE, 27(2), 224-227(2005)
  16. Hong, S. Y., Kim, S. C., Yoon, Y. S., Park, S. K., Kim, K. H. and Hwang, S. R., 'The Analysis and Leaching Characteristics of Organic Compounds in Incineration Resiudes from Municipal Solid Waste Incinerators,' Anal. Sci. Technol., 19(1), 86-95(2006)
  17. Kang, J. W., Lee, K. H. and Lee, M. J., 'Application of Radiation, Ultraviolet and Ultrasound Irradiation Process for Wastewater Treatment,' J. KSSE, 19(1), 111-120(1997)
  18. Mason, T. J., 'Sonochemistry: the use of Ultrasound in Chemistry,' Royal Soc. Chem., 1-8(1990)
  19. Al-Ekabi, H., Butters, B. and Delany, D., Photocatalytic Purification and Treatment of Water and Air, D.F. Ollis and H. Al- Ekabi(Ed.,), Elsevier Science Publishers, B.V., 321(1993)
  20. Yue, P. L. and Legrini, O., AlChE Natl. Meeting, San Francisco, 1989