The Korean Journal of Pesticide Science (농약과학회지)

The Korean Society of Pesticide Science (한국농약과학회)
권호 표지

Establishment of Analytical Method for Cyprodinil Residue In Apple, Mandarin, Korean Cabbage and Green Pepper

HPLC를 이용한 사과, 감귤, 배추, 고추 중 살균제 Cyprodinil의 분석법 확립

  • 이혜리 (서울대학교 농생명공학부) ;
  • 류명주 (서울대학교 농생명공학부) ;
  • 김은혜 (서울대학교 농생명공학부) ;
  • 문준관 (서울대학교 농생명공학부) ;
  • 도정아 (식품의약품안전평가원 화학물질과) ;
  • 오재호 (식품의약품안전평가원 화학물질과) ;
  • 권기성 (식품의약품안전평가원 화학물질과) ;
  • 임무혁 (식품의약품안전청 식품기준과) ;
  • 이영득 (대구대학교 생명환경학부) ;
  • 김정한 (서울대학교 농생명공학부)
  • Received : 2010.12.09
  • Accepted : 2010.12.18
  • Published : 2010.12.31
Download PDF
⟨ Previous Next ⟩

Abstract

This study was performed to develop a precise single residue analytical method of fungicide cyprodinil in representative crops for using as general residue analytical methods which could be applied to most of crops. Apple, mandarin, Korean cabbage and green pepper were selected as representative crops, and they were macerated, extracted with acetonitrile, concentrated and partitioned with n-hexane. Then the extracts were concentrated and cleaned-up through silica gel column with ethyl acetate:n-hexane (15:85, v/v) before concentration and analysis with HPLC. LOQ (limit of quantitation) of cyprodinil was 5 ng (S/N>10) and MQL (method qnantitation limit) was 0.05 mg/kg. Recoveries were measured at three fortification levels (MQL, 10MQL and 100MQL) on crop samples and ranged from 82.0 to 108.2% and coefficients of variation were less than 10% regardless of sample type.

본 연구는 살균제 cyprodinil의 잔류분석을 대부분의 해당 농작물에 적용할 수 있도록 대표 작물을 선발하고, 회수율을 포함한 분석법 검증을 통하여 cyprodinil의 단성분 정밀 분석법을 개발하였다. 대표 작물로는 사과, 감귤, 배추, 고추를 선정하였고, 마쇄한 농작물 시료에 acetonitrile을 가한 후 진탕하여 잔류물을 추출하였다. 추출액을 감압농축 한 뒤, 농축물을 포화식염수와 증류수로 희석하고 n-hexane으로 분배하였다. 분배액을 농축하고 ethyl acetate:n-hexane 혼합액(15:85, v/v)으로 용리하는 silica gel 크로마토그래피법으로 정제 후, 농축하여 HPLC로 분석하는 방법을 확립하였다. Cyporidnil의 정량한계(LOQ : limit of quantitation)는 5 ng(S/N>10) 이었고, 분석정량한계(MQL : method quantitation limit)는 0.05 mg/kg이었다. 무처리 시료에 cyprodinil 표준용액을 3수준(MQL, 10MQL과 100MQL) 3반복으로 처리하여, 확립된 전체 분석과정을 이용하여 회수율을 산출한 결과는 82.0~108.2%이었으며, 농산물 시료에 관계없이 반복 간 분석오차는 10% 미만이었다.

Keywords

References

  1. Cabras P., A. Angioni, V.L. Garau, M. Melis, F.M. Pirisi, E.V. Minelli, F. Cabitza and M. Cubeddu (1997) Fate of some new fungicides (cyprodinil, fludioxonil, pyrimethanil, and tebuconazole) from vine to wine. J. Agric. Food Chem. 45(7):2708-2710. https://doi.org/10.1021/jf960939x
  2. Dec J., K. Haider, A. Benesi, V. Rangaswamy, A. Schaffer, U. Plucken and J. M. Bollag (1997) Analysis of soil-bound residues of $^{13}C$-labeled fungicide cyprodinil by NMR spectroscopy. Environ. Sci. Technol. 31:1128-1135. https://doi.org/10.1021/es960631m
  3. Fong, W. G, H. A. Moye, J. N. Seiber and J. P. Toth (1999) Pesticide Residues in food: Methods, Technologies, and Regulations. Wiley Interscience. pp. 3-4, 40-44, Canada.
  4. Garau V. L., A. Angioni, A. Aguilera, A. A. Del Real, M. Russo and P. Cabras (2002) Disappearance of azoxystrobin, pyrimethanil, cyprodinil, and fludioxonil on tomatoes in a greenhouse. J Agric Food Chem 50:1929-1932. https://doi.org/10.1021/jf011219f
  5. Heye, U.J., J. Speich, H. Siegle, R. Wohlhauser and A. Hubele (1994) CGA 219417-a novel broad-spectrum fungicide. Proc. Brighton Crop Prot. Conf. Pests Dis. 2:501-8.
  6. Knight S. C., V. M. Anthony, A. M. Brady, A. J. Greenland, S. P. Heaney, D. C. Murray, K. A. Powell, M. A. Schulz, C. A. Spinks, P. A. Worthington and D. Youle (1997) Rationale and perspectives on the development of fungicides. Annu. Rev. Phytopathol. 35:349-72. https://doi.org/10.1146/annurev.phyto.35.1.349
  7. Liu, C., S. Wang, L. Li, H. Zhao, S. Jiang and F. Liu (2010) Analysis of cyprodinil in leek and pepper and its decline under field condition. Environ. Monit. Assess. DOI: 10.1007/s10661-010-1730-y
  8. Marin A., J. Oliva, C. Garcia, S. Navarro and A. Barba (2003) Dissipation rates of cyprodinil and fludioxonil in lettuce and table grape in the field and under cold storage conditions. J. Agric. Food Chem. 51:4708-4711. https://doi.org/10.1021/jf021222e
  9. McNair, H. M. and J. M. Miller (1997) Basic Gas Chromatography. pp.7, 51, Wiley Interscience, U.S.A.
  10. Miller, J. M. (2005) Chromatography : concepts and contrasts (2nd), Wiley Intersciense, pp. 286-287, U.S.A.
  11. Moon J. K., H. J. Lee, Y. W. Kim, Y. H. Lee and J. H. Kim (2003) Establishment of pre-harvest interval for cyprodinil in grape. Agric. Chem. Biotechnol. 46(4):174-176.
  12. Pose-Juan E., B. Cancho-Grande, R. Rial-Otero and J. Simal- Gandara (2006) The dissipation rates of cyprodinil, fludioxonil, procymidone and vinclozoline during storage of grape juice. Food Control 17:1012-1017. https://doi.org/10.1016/j.foodcont.2005.07.009
  13. Rood, D. (2007) The Troubleshooting and Maintenance Guide for Gas Chromatographyers pp. 15-17, p. 22, Wiley-VCH, U.S.A.
  14. Tomlin, C. D. S. (2006) The Pesticide Manual (14th), pp. 264-266, British Crop Production Council, UK.
  15. Vaquero-Ferna'ndez L., A. Sa'enz-Herna'ez, J. Sanz-Asensio, P. Ferna'ndez-Zurbano, M. Sainz-Ram'rez, B. Pons-Jubera, M. Lo'pez-Alonso, S. Epifanio-Ferna'ndez and M. Mart'nez-Soria (2008) Determination of cyprodinil and fludioxonil in the fermentative process of must by high-performance liquid chromatography-diode array detection. J Sci. Food Agric. 88:1943-1948. https://doi.org/10.1002/jsfa.3301
  16. 農薬殘留分析研究班 (2006) 最新農薬 の殘留分析殘留分析 [改訂版], pp. 252-253, 中央法規出版
  17. 김강진, 김하석, 이대운, 이원 (1997) 분석화학 (제4판), pp. 698, 자유아카데미.
  18. 식품의약품안전청 (2010a) 식품의 농약 잔류허용기준.
  19. 식품의약품안전청 (2010b) 식품공전
  20. 이영득 (2009) 식품공전 잔류농약분석법 실무 해설서 pp. 3, 78-79, 식품의약품안전청.
  21. 이종화, 박희원, 금영수, 권찬혁, 이영득, 김정한 (2008) 시설 내 오이재배 중 살균제 Boscalid의 잔류특성. 농약과학회지 12(1):67-73.
  22. (주)랩프런티어 (2004) 식품 중 동시다성분 분석법 개선 연구 pp. 89, 114 식품의약품안전청.
  23. 한국작물보호협회 (2010) 농약사용지침서, 삼정인쇄공사 pp. 144-145.