Journal of Dairy Science and Biotechnology

Korean Society of Dairy Science and Biotechnology (한국낙농식품응용생물학회)
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Comparative Evaluation of the Analytical Methods used to Determine Pesticide Residues in Milk via Dispersive Solid Phase Extraction

Dispersive Solid Phase Extraction을 사용한 우유 내 잔류농약 다성분 동시 분석법 비교연구

  • 오남수 (서울우유협동조합 중앙연구소) ;
  • 신용국 (서울우유협동조합 중앙연구소) ;
  • 이지영 (서울우유협동조합 중앙연구소) ;
  • 백승천 (서울우유협동조합 중앙연구소)
  • Received : 2015.03.01
  • Accepted : 2015.03.15
  • Published : 2015.03.31
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Abstract

The aim of this study was to optimize a simple, fast, and economic analytical method for the simultaneous determination of various pesticides (aldrin, p,p'-DDT, o,p'-DDT, p,p'-DDE, ${\alpha}$-endosulfan, ${\beta}$-endosulfan, dieldrin, heptachlor, permethrin, chlordane, deltamethrin, diazinon, bifenthrin, methoprene, propargite, fenpropathrin, cypermethrin, fenvalerate, and fenpropathrin) in milk by using dispersive solid phase extraction (SPE). In this study, two different extraction methods (low temperature cleanup and liquid-liquid partitioning), which were followed by a cleanup process based on dispersive-SPE, were evaluated and compared for the 19 pesticides. The results for all the pesticides were determined by gas chromatography mass spectrometry (GC/MS) with selected-ion monitoring mode, and the matrix effect of the method was evaluated. Comparison of these approaches yielded higher and more consistent recoveries of most pesticides at fortification levels of $1{\mu}g/mL$ using low-temperature fat precipitation, followed by cleanup process based on dispersive-SPE with PSA and C18 as sorbents, than other preparation process. The relative standard deviation was <20 % and the combination of this method were very effective for the cleanup.

본 연구에서는 dispersive-SPE를 사용하여 간편하고, 신속하며, 경제적인 우유 내 19종 잔류농약의 동시 다성분 분석법을 설정하고자 하였다. Liquid-liquid partitioning method와 low-temperature cleanup method를 적용한 추출방법과 PSA 및 PSA + C18의 sorbent가 사용된 dispersive-SPE를 사용한 정제방법을 비교 실험하였으며, GC/MS의 선택이온 검색법(selected ion monitoring, SIM)으로 정량 분석하였다. matrix-matched standards와 matrix-free standards를 사용하여 분석방법의 matrix enhancement effect를 확인하였고, 분석방법 설정을 위한 비교실험의 결과, low-temperature cleanup 방법으로 추출하여 dispersive-SPE(PSA + C18)로 정제하는 방법이 시료 추출물의 간섭물질을 제거하는데 가장 효과적이고, 첨가한 $1{\mu}g/mL$에 대한 개별 농약 성분의 회수율 또한 전체적으로 가장 높은 수준을 나타내었으며, 모든 농약 성분의 RSD(%)가 20% 이하로서 기준에 적합한 재현성을 나타내었다.

Keywords

References

  1. Albero, B., Sanchez-Brunete, C. and Tadeo, J. L. 2005. Multiresidue determination of pesticides in juice by solidphase extraction and gas chromatography-mass spectrometry. Talanta. 66(4):917-924. https://doi.org/10.1016/j.talanta.2004.12.046
  2. Albero, B., Sanchez-Brunete, C., Donoso, A. and Tadeo, J. L. 2004. Determination of herbicide residues in juice by matrix solid-phase dispersion and gas chromatographymass spectrometry. J. Chromatogr. A. 1043(2):127-133. https://doi.org/10.1016/j.chroma.2004.05.097
  3. Anastassiades, M., Lehotay, S. J., Stajnbaher, D. and Schenck, F. J. 2003. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce. J. AOAC Int. 86(2):412-431.
  4. Anastassiades, M., Mastovska, K. and Lehotay, S. J. 2003. Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides. J. Chromatogr A. 1015(1-2):163-184. https://doi.org/10.1016/S0021-9673(03)01208-1
  5. Battu, R. S., Singh, B. and Kang, B. K. 2004. Contamination of liquid milk and butter with pesticide residues in the Ludhiana district of Punjab state, India. Ecotoxicol. Environ. Saf. 59(3):324-331. https://doi.org/10.1016/j.ecoenv.2003.08.017
  6. Campoy, C., Jimemz, M., Olea, S., Moreno, M., Canabate, F., Olea, N., Bayes, R. and Molina-Font, J. A. 2001. Analysis of organochlorine pesticides in human milk: Preliminary results. Early Human Development 65:S183-S190. https://doi.org/10.1016/S0378-3782(01)00221-3
  7. Consuelo, S. B., Beatriz, A., German, M. and Jose, L. 2005. Determination of pesticides by GC/MS using analyte protectants to counteract matrix effect. Anal. Sci. 21:1291-1296. https://doi.org/10.2116/analsci.21.1291
  8. Darko, G. and Acuaah, S. O. 2007. Levels of organochlorine pesticides residues in dairy products in Kumasi, Ghana. Chemosphere 71(2):294-298.
  9. Egea Gonzalez, F. J., Hernandez Torres, M. E., Almansa Lopez, E., Cuadros-Rodriguez, L. and Martinez Vidal, J. L. 2002. Matrix-effects of vegetable commodities in electroncapture detection applied to pesticide multiresidue analysis. J. Chromatogr. A. 966(1-2):155-165. https://doi.org/10.1016/S0021-9673(02)00707-0
  10. European Union (2007) Method validation and quality control procedures for pesticide residues analysis in food and feed (Document No. SANCO/10232/2006). Available from : http://ec.europa.eu/food/plant/protection/resources/qualcontrol_en.pdf
  11. Godula, M., Hajslova, J. and Alterova, K. 1999. Pulsed splitless injection and the extent of matrix effects in the analysis of pesticides. J. High Res. Chromatogr. 22:395-402. https://doi.org/10.1002/(SICI)1521-4168(19990701)22:7<395::AID-JHRC395>3.0.CO;2-O
  12. Hercegova, A., Domotorova, M. and Matisova, E. 2007. Sample preparation methods in the analysis of pesticide residues in baby food with subsequent chromatographic determination. J. Chromatogr. A. 1153(1-2):54-73. https://doi.org/10.1016/j.chroma.2007.01.008
  13. Lehotay, S. J., Mastovska, K. and Yun, S. J. 2005. Evaluation of two fast and easy methods for pesticide residue analysis in fatty food matrixes. J. AOAC. Int. 88(2):630-638.
  14. Lehotay, S. J., Lightfield, A. R., Harman-Fetcho, J. A. and Donoghue, D. J. 2001. Analysis of pesticide residues in eggs by direct sample introduction/gas chromatography/tandem mass spectrometry. J. Agric. Food Chem. 49(10):4589-4596. https://doi.org/10.1021/jf0104836
  15. Lentza-Rizos, C. H., Avramides, E. J. and Cherasco, F. 2001. Low-temperature clean-up method for the determination of organophosphorus insecticides in olive oil. J. Chromatogr A. 912(1):135-142. https://doi.org/10.1016/S0021-9673(01)00527-1
  16. MacMahon, B. M. and Wagner, R. F. (1994, revised 1996). Pesticide analytical manual. Volume 1, 3rd ed. U.S. FDA.
  17. Sanchez-Brunete, C., Albero, B. and Tadeo, J. L. 2004. Multiresidue determination of pesticides in soil by gas chromatography-mass spectrometry detection. J. Agric. Food Chem. 52(6):1445-1451. https://doi.org/10.1021/jf0354646
  18. Schenck, F. J. and Lehotay, S. J. 2000. Does further clean-up reduce the matrix enhancement effect in gas chromatographic analysis of pesticide residues in food? J. Chromatogr. A. 868:51-61. https://doi.org/10.1016/S0021-9673(99)01137-1