A Study on the Degradation Mechanism of Diazinon and the Acute Toxicity Assessment in Photolysis and Photocatalysis

광반응과 광촉매 반응을 이용한 Diazinon 농약의 분해 기전과 독성 평가에 관한 연구

  • Oh, Ji-Yoon (Department of Environmental Health, School of Public Health, Seoul National University) ;
  • Kim, Moon-Kyung (Department of Environmental Health, School of Public Health, Seoul National University) ;
  • Son, Hyun-Seok (Department of Environmental Health, School of Public Health, Seoul National University) ;
  • Zoh, Kyung-Duk (Department of Environmental Health, School of Public Health, Seoul National University)
  • 오지윤 (서울대학교 보건대학원 환경보건학과) ;
  • 김문경 (서울대학교 보건대학원 환경보건학과) ;
  • 손현석 (서울대학교 보건대학원 환경보건학과) ;
  • 조경덕 (서울대학교 보건대학원 환경보건학과)
  • Published : 2008.11.30


Diazinon is a phosphorothiate insecticide widely used in the world including Korea. This study investigates the feasibility of photolysis and photocatalysis processes for the degradation of diazinon in water. Both photolysis and photocatalysis reactiosn were effective in degrdading diazinon, however lower TOC removals were achieved. In case of photocatalysis, approximately 40% of nitrogen from diazinon was recovered as NO$_3^-$, and less than 5% of phosphorus as PO$_4{^{3-}}$. However, the sulfur in diazinon molecule was completely recovered to SO$_4{^{2-}}$ from photocatalysis reaction, and the recovery from photolysis was 50%, indicating that P=S bond easily breaks first during photolysis and photocatalysis. The poor recoveries of ionic byproducts and TOC from photolysis and photocatalysis indicate the presence of other organic intermediates during reactions. The formation of organic intermediates were identified during reactions using GC/MS and LC/MS/MS, and the main degradation products were diazoxon, and 2-isopropyl-4-methyl-6-hydroxypyrimidine (IMP), respectively. Finally, the acute 48-hr toxicity test using Daphnia magna were employed to measure the toxicity reduction during photocatalysis of degradation. The results showed that the toxicity increased until 180 min of the photocatalysis reaction (from EC$_{50}$ (%) of 69.6 to 13.2%), however, acute toxicity completely disappeared (>100%) after 360 min. The toxicity results showed that the intermediates from photocatalysis such as diazoxon were more toxic than diazinon itself, however these intermediates can be degraded or mineralized with further reaction.


  1. Bolognesi, C., Morasso, G., "Genotoicity of pesticides: potential risk for consumers," Trends Food Sci. Technol., 11, 182-187(2000) https://doi.org/10.1016/S0924-2244(00)00060-1
  2. Wang, Q., Lemley, A. T., "Oxidation of diazinon by anodic fenton treatment," Water Res., 36, 3237-3244(2002) https://doi.org/10.1016/S0043-1354(02)00041-6
  3. Worthing, C. R., Hance, R. J., "The pesticide manual 9th ed. surrey," UK: The british crop protection council, 243-244(1991)
  4. 농약연보, 농약공업협회(2005)
  5. Ansari, B. A., Kumar, K., "Diazinon toxicity: effect on protein and nucleic acid metabolism in the liver of zebrafish, brachydanio rebio (cyprinidae)," Sci. Total Environ., 76, 63-68(1988) https://doi.org/10.1016/0048-9697(88)90284-7
  6. 류성필, 오윤근, "$TiO_2$ 광촉매를 이용한 diazinon의 광분해에 관한 연구," 한국환경과학회지, 9(2), 151-158(2000)
  7. Hamm, J. T., Hinton, D. E., "The role of development and duration of exposure to the embryotoxicity of diazinon," Aquat. Toxicol., 48, 403-418(2000) https://doi.org/10.1016/S0166-445X(99)00065-X
  8. Eisler, R. "Diazinon hazards to fish, wildlife, and invertebrates: a synoptic review," U.S. Fish and Wildlife Service, U.S. Dep. Int. Washington D.C. 85, No. (1-9), 1-38(1986)
  9. Burkepile, D. E., Moore, M. T., Holland, M. M., "The susceptibility of five nontarget organims to aqueous diazinon exposure," Bull. Environ. Contam. Toxicol., 64, 114-121(2000) https://doi.org/10.1007/s001289910018
  10. 농림부, 잔류농약안정성조사(2006)
  11. 이서래, 김용화, 이미경, "수질중의 농약잔류 허용기준 설정을 위한 근거자료," Korean J. Environ. Agric., 14(3), 351-373(1995)
  12. Baily, H., Deanovic, L., Reyes, E., Kimball, T., Larson, K., Cortright, K., Connor, V., and Hinton, D., "Diazinon and Chlorpyrifos in Urban Waterways in Northern California, USA," Environ. Toxicol. Chem., 19, 82-87 (2000) https://doi.org/10.1897/1551-5028(2000)019<0082:DACIUW>2.3.CO;2
  13. 환경부, 먹는물수질기준 등에 관한 규칙(1999)
  14. Fulton, M. H., Key, P. B., "Acetylcholinesterase inhibition in estuarine fish and invertebrates as an indicator of organophosphorus insecticide exposure and effects," Environ. Toxicol. Chem., 20, 37-45(2001) https://doi.org/10.1897/1551-5028(2001)020<0037:AIIEFA>2.0.CO;2
  15. Oruc, E. O., Ustaa, D., "Evaluation of oxidative stress responses and neurotoxicity potential of diazinon in different tissues of Cyprinus carpio," Environ. Toxicol. Pharmacol., 23(1), 48-55(2006) https://doi.org/10.1016/j.etap.2006.06.005
  16. 국립독성연구원 독성물질정보검색 http://kntp.nitr.go.kr/
  17. Behnajady, M. A., Modirshahlaa, N., and Shokri, M., "Photodestruction of Acid Orange 7 in aqueous solutions by $UV/H_2O_2$: influence of operational parameters," Chemosphere, 55, 129-134(2004) https://doi.org/10.1016/j.chemosphere.2003.10.054
  18. Zoh, K. D., Stenstrom, M. K., "Fenton oxidation of hexahydro 1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)," Water Res., 36, 1331-1341(2002) https://doi.org/10.1016/S0043-1354(01)00285-8
  19. Mattews, R. W., "Photo-oxidation of organic material in aqueous of $TiO_2$," Water Res., 20, 569-578(1986) https://doi.org/10.1016/0043-1354(86)90020-5
  20. Daneshvara, N., Behnajadyb, M. A., Asghar, Y. Z., "Photooxidative degradation of 4-nitrophenol (4-NP) in $UV/H_2O_2$ process: Influence of operational parameters and reaction mechanism," J. Hazard. Mater., 139(2), 275-279(2007) https://doi.org/10.1016/j.jhazmat.2006.06.045
  21. Haag, W. R., Johnson, M. G., Scofield, R., "Direct photolysis of trichloroethylene in air: effect of cocontaminant toxicity, of products, and hydrothermal treatment of products," Environ. Sci. Technol., 30(2), 414-421(1996) https://doi.org/10.1021/es950047y
  22. Shen, Y. S., Ku, Y., "Decomposition of gas-phase trichloroethene by the $UV/TiO_2$ process in the presence of ozone," Chemosphere, 46(1), 101-107(2002) https://doi.org/10.1016/S0045-6535(00)00585-3
  23. Rosenfeldta, E. J., Linden, K. G., Canonicaa, S., Guntena, U. V., "Comparison of the efficiency of OH radical formation during ozonation and the advanced oxidation processes $O_3/H_2O_2$ and UV/H2O2," Water Res., 40(20), 3695-3704(2006) https://doi.org/10.1016/j.watres.2006.09.008
  24. Changa, M. C., Shu, H. Y., and Yu, H. H., "An integrated technique using zero-valent iron and $UV/H_2O_2$ sequential process for complete decolorization and mineralization of C. I. Acid Black 24 wastewater," J. Hazard. Mater., 138(3), 574-581(2006) https://doi.org/10.1016/j.jhazmat.2006.05.088
  25. Venkatadri, R. and Peters, R. W., "Chemical oxidation technologies: ultraviolet light/hydrogen peroxide, Fenton's reagent, and titanium dioxide-assisted photocatalysis," J. Hazard. Mater., 10, 107-149(1993)
  26. Choi, J. K., Son, H. S., Kim, T. S., Stenstrom, M. K., and Zoh, K. D., "Degradation Kinetics and Mechanism of RDX and HMX in $TiO_2$ Photocatalyst," Environ. Technol., 27(2), 219-232(2006) https://doi.org/10.1080/09593332708618636
  27. Kim, T. S., Kim, J. G., Choi, K. H., Stenstrom, M. K., and Zoh, K. D., "Degradation Mechanism and the Toxicity Assessment in $TiO_2$ Photocatalysis and Photolysis of Parathion," Chemosphere, 63(6), 926-933(2006) https://doi.org/10.1016/j.chemosphere.2005.09.036
  28. Hillar, S. and Linden, K. G., "Degradation and byproduct formation of diazinon in water during UV and $UV/H_2O_2$ treatment," J. Hazard. Mater., 52, 7-13(2006)
  29. Kouloumbos, V. N., Tsipi, D. F., Hiskia, A. E., Nikolic, D., and Van Breemen, R. B., "Identification of photocatalytic degradation products of diazinon in $TiO_2$ aqueous suspensions using GC/MS/MS and LC/MS with quardrupole time-of-flight mass spectrometry," J. Am. Soc. Mass Spectrom., 14, 803-817(2003) https://doi.org/10.1016/S1044-0305(03)00333-7
  30. Ku, Y., Chang, J. L., Shen, Y. S., and Lin, S. Y., "Decomposition of diazinon in aqueous solution by ozonation," Water Res., 32(6), 1957-1963(1998) https://doi.org/10.1016/S0043-1354(97)00353-9
  31. Pesticide Action Network International web, logged on, http://www. pesticideinfo.org/Detail_Chemical.jsp
  32. Pesticide Action Network International web, http://www. pan-uk.org/pestnews/Actives/diazinon.htm, logged on April (2007)
  33. Zhang, Q. and Pehkonen, S. O., "Oxidation of diazinon by aqueous chlorine: kinetics, mechnisms, and product studies," J. Agric. Food Chem., 47, 1760-1766(1999) https://doi.org/10.1021/jf981004e
  34. Diego, M. M., Gerard, M., Estrella, F. J., Luis, A., Ram6n, A., and Margarita, M., "Simazine Degradation by Immobilized and Suspended Soil Bacterium," International Biodeterioration & Biodegradation, 40(2-4), 93-99(1997) https://doi.org/10.1016/S0964-8305(97)00049-8
  35. Tohru, K., Linxian, D., Makiko, Y., and Masao, Y., "Biodegradation of an s-triazine herbicide, simazine," J. Molecular Catal. B: Enzymatic, 11, 1073-1078(2001) https://doi.org/10.1016/S1381-1177(00)00169-7
  36. U.S. EPA http://cfpub.epa.gov/ecotox/logged on June(2007)
  37. Allender W. J. and Britt A. G., "Analysis of liquid formulations and breakdown products: an austrailia-wide survey," Environmental Contamination Toxicology, 53, 902-906(1994)