태양광 $TiO_2$ 광촉매를 이용한 Parathion의 분해와 독성저감에 관한 연구

A Study on the Degradation of Parathion and Reduction of Acute Toxicity in Solar $TiO_2$ Photocatalysis

  • 김탁수 (서울대학교 보건환경연구소) ;
  • 김정곤 (서울대학교 보건환경연구소) ;
  • 최경호 (서울대학교 보건환경연구소) ;
  • 조경덕 (서울대학교 보건환경연구소)
  • Kim, Tak-Soo (Institute of Environmental Health, School of Public Health, Seoul National University) ;
  • Kim, Jung-Kon (Institute of Environmental Health, School of Public Health, Seoul National University) ;
  • Choi, Kyung-Ho (Institute of Environmental Health, School of Public Health, Seoul National University) ;
  • Zoh, Kyung-Duk (Institute of Environmental Health, School of Public Health, Seoul National University)
  • 발행 : 2005.08.31

초록

본 연구에서는 대표적인 유기인계 농약인 parathion을 대상으로 태양광의 조사 하에 $TiO_2$ 광촉매반응과 광반응에 의한 처리를 수행하였다. 실험의 결과 $TiO_2$ 광촉매반응이 광반응과 $TiO_2$ 흡착 조건에 비하여 효과적으로 parathion을 제거시켰다. 10 mg/L의 parathion은 90분 이내에 광촉매 반응으로 완전히 제거되었으며 반응시간 150분 후에 TOC는 약 63% 정도 감소되었다. 광촉매 반응에 의한 parathion의 분해에 따라, 질소 형태의 이온 부산물은 ${NO_2}^-$, ${NO_3}^-$, 그리고 ${NH_4}^+$가 발견이 되었고, 황은 ${SO_4}^{2-}$로 약 80%, 그리고 인은 ${PO_4}^{3-}$로 5% 이하로 회수되었다. 또한 parathion의 분해시 유기중간 생성물은 paraoxon과 4-nitrophenol 등이 측정되었으며, 이들 부산물들은 반응이 진행되어 가며 계속 분해됨을 보였다. 광촉매 반응과 광반응에 의하여 처리된 용액의 독성의 감소를 평가하기 위하여 두 가지 생물종인 V. fischeri와 D. magna를 이용하여 처리수의 급성 독성의 감소를 알아보았다. 두 가지 생물종 모두 광촉매반응 조건에서는 처리수의 상대독성이 초기에 비해 반응시간 150분 후에 거의 모두 감소되었고, 광반응 조건에서는 V. fischeri와 D. magna 각각에 대해서 76%와 57%의 상대독성 감소가 관찰되었다. Parathion과 TOC의 감소와 급성독성의 저감양상은 유사한 경향을 보였다.

The photocatalytic degradation of methyl parathion was carried out using a circulating $TiO_2$/solar system. Under the photocatalytic condition, parathion was more effectively degraded than by the photolysis or $TiO_2$ only condition. The parathion degradation followed pseudo first-order kinetics. With photocatalysis, 10 mg/L parathion was completely degraded within 90 min with a TOC decrease exceeding 63% after 150 min. The nitrogen from parathion was recovered mainly as ${NO_2}^-$, ${NO_3}^-$, and ${NH_4}^+$, 80% of sulfur as ${SO_4}^{2-}$, and less than 5% of phosphorus as ${PO_4}^{3-}$ during photocatalysis. The organic intermediates 4-nitrophenol and paraoxon were also identified, and these were further degraded. Two different bioassays using V. fischeri and D. magna were employed to measure the toxicity reduction in the solutions treated by both photocatalysis and photolysis. Relative toxicity was reduced almost completely after 150 min in both organisms under the photocatalysis, whereas in photolysis, 76 and 57% reduction was achieved for V. fischeri and D. magna, respectively. The acute toxicity reduction pattern corresponded with the decrease in parathion and TOC concentrations.

키워드

참고문헌

  1. lnterim reregistration eligibility document for methyl parathion, Office of Prevention, Pesticides and Toxic substances US EPA
  2. Korea Ministry of Environment Home Page
  3. Decision Guidance Document for acutely hazardous pesticides or concern to human health under condilions or use in developing countries (PIC) FAO
  4. Arch. Environ. Contam. Toxicol. v.45 Acute Toxicity of Methyl Parathion in Wetland mesocosms: Assessing the Influence of Aquatic Plants Lsing Laboratory Testing with Hyalella azteca Schulz. R.;Moore, M.T.;Bennett, E.R.;Milam, C.D.;Bouldin, J.L.;Farris, J.L.;Smith S. Jr.;Cooper, C.M.
  5. J. Loss Prevention in the Process Industries v.13 Thermal decomposition of ethyl and methyl parathion Germain, A.;Bizzarri, D.;Dodet, C. https://doi.org/10.1016/S0950-4230(99)00067-4
  6. Applied Catalysis B: Environmental v.42 Etfect of operating parameters on the testing of new industrial titania catalysts at solar pilot plant scale Malato, S.;Blanco, J.;Campos, A.;Cacers, J.;Guillard, C.;Herrmann, J.M.;Fernandez-Alba, A.R. https://doi.org/10.1016/S0926-3373(02)00270-9
  7. MicrotoxTM manual: a toxicity testing handbook, volume II detailed protocols Microbics Corp.
  8. Method for measuring the acute toxicity of effluents and receiving water to fershwater and marine organisms;EPA/821/R- 02/012 US EPA
  9. Applied Catalysis B: Environmental v.42 Pholocalalylic transformation of pesticides in aqueous titanium dioxide suspensions using artificial and solar light intermediates and degradation pathways Konstantinou, I.K.;Albanis, T.A. https://doi.org/10.1016/S0926-3373(02)00266-7
  10. Water Sci. Technol. v.46 Photocatalytic degradation of explosives contaminated water Lee, S.J.;Son, H.S.;Lee, H.K.;Zoh, K.D.
  11. J. Chem. Soc. Faraday Trans. v.93 Photocatalytic interconversion of nitrogen-containing benzene derivatives Piccinini, P.;Minero, C.;Vincenti, M.;Pelizzetti, E. https://doi.org/10.1039/a607883d
  12. Analytica. Chimica. Acta. v.467 Application of solid-phase rnicroextraction for monitoring the photocatalytic decomposition of tenthion and parathion in aqueous $TiO_2$ suspensions Sakkas, V.A.;Lambropoulou, D.A.;Sakellarides, T.M.;Albanis, T.A. https://doi.org/10.1016/S0003-2670(02)00090-9
  13. J. Photochem. Photobiol. A: Chem. v.116 Photodegradation of parathion in titanium dioxide and zero valent iron solutions in the presence of hydrogen peroxide Doong, R.A.;Chang, W.H. https://doi.org/10.1016/S1010-6030(98)00292-5
  14. Water Research v.36 Toxicity assays: a way for evaluating AOPs efficiency Fernandez-Alba. A.R.;Hernando, D.;Aguera, J.;Caceres, J.;Malato, S. https://doi.org/10.1016/S0043-1354(02)00165-3
  15. Mat. Sci. Engineering C v.21 A comparative photodegradation studies of methyl parathion by using ?Lurnistox test and conductometric biosensor technique Dzyadevych, S.V.;Chovelon, J.M. https://doi.org/10.1016/S0928-4931(02)00058-9
  16. Aquatic Toxicology v.30 Toxicity of organophosphate insecticides and their metabolites to water flea Daphnia magna, the Microtox test and an acetylcholinesterase inhibition test Galli, R.;Rich, H.W.;Scholts, R. https://doi.org/10.1016/0166-445X(94)90063-9