Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

The Korean Society of Food Hygiene and Safety (한국식품위생안전성학회)
권호 표지
DOI QR코드

DOI QR Code

Development of an Analytical Method for Chloropicrin Determination in Hulled Rice by GC-ECD and GC-MS

GC-ECD 및 GC-MS를 이용한 현미 중 chloropicrin의 잔류시험법 개발

  • Do, Jung-Ah (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, MFDS) ;
  • Choi, Jeong-Heui (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, MFDS) ;
  • Park, Hyejin (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, MFDS) ;
  • Park, Yong-Chun (New Hazardous Substances Team, National Institute of Food and Drug Safety Evaluation, MFDS) ;
  • Yoon, Hae-Jung (Hazardous Substances Analysis Division, Seoul Reginal Food and Drug Administration, MFDS) ;
  • Choi, Dongmi (Novel Food Division, Food Nutrition and Dietary Safety Bureau, MFDS) ;
  • Oh, Jae-Ho (Food Safety Risk Assessment Division, National Institute of Food and Drug Safety Evaluation, MFDS)
  • 도정아 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 최정희 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 박혜진 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 박용춘 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 신종유해물질팀) ;
  • 윤혜정 (식품의약품안전처 서울지방청 유해물질분석과) ;
  • 최동미 (식품의약품안전처 식품영양안전국 신소재식품과) ;
  • 오재호 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 식품위해평가과)
  • Received : 2013.02.19
  • Accepted : 2013.07.29
  • Published : 2013.09.30
Download PDF
⟨ Previous Next ⟩

Abstract

A simple and sensitive analytical method was developed using gas chromatograph with electron capture detector (GC-ECD) and gas chromatograph-mass spectrometer (GC-MS) for determination and identification of chloropicrin. Because of small molecular weight and high volatile properties of chloropicrin, analytical method was developed utilizing headspace extraction and direct injection to the GC. The developed method was validated using hulled rice sample spiked with chloropicrin at different concentration levels, 0.1 and 0.5 mg/kg. Average recoveries of chloropicrin (using each concentration three replicates) ranged 77.7~79.3% with relative standard deviations less than 10% and calibration solutions concentration in the range $0.005{\sim}0.5{\mu}g/mL$, and limit of detection (LOD) and limit of quantification (LOQ) were 0.004 and 0.01 mg/kg, respectively. The result showed that developed analytical methods was successfully applied to detect a small amount of chloropicrin in hulled rice.

Chloropicrin은 국내에서는 사용되지 않으며, 잔류허용기준이 불검출로 설정된 농약이다. 그러나 중국에서는 훈증제, 살균제, 살선충제 및 저장 곡물의 살충제로 사용되고 있으며, 잔류허용기준이 설정되어 있다. 따라서 본 연구에서는 중국 등에서 수입하는 식품 중 국내에서 사용하지 않는 농약에 대한 안전성을 확보하기 위하여 해당 농약을 신속하고 빠르게 검출할 수 있는 시험법을 개발하고자 하였다. Chloropicrin은 분자량이 작고 휘발성이 큰 화합물이므로 헤드스페이스 추출법을 활용하여 검체 추출액을 직접 GC에 주입하는 시험법을 개발하였으며, 확립된 시험법을 검증한 결과 회수율이 77.7~79.3%로 조사되어 코덱스 국제가이드라인(CAC/GL 40)에 적합함을 확인하였다. 정량한계 또한 0.05 mg/kg 이하로 매우 우수한 감도를 가지고 있음을 확인하였으며, GC-MS를 이용한 재확인과정을 추가로 확립하여 본 시험법의 신뢰도를 높였다. 확립된 시험법은 식품에 잔류할 수 있는 농약의 기준 준수여부에 대한 적합성을 판단하기 위한 공정시험법으로 활용되고 있다.

Keywords

References

  1. Wilhelm S.N. : Chloropicrin as a Soil Fumigant. Niklor Chemical Company, Inc., Chairman, Chloropicrin Manufacturers Task Force, Long Beach, CA 90810-1695. Available at http:// www.ars.usda.gov/is/np/mba/july96/wilhel1.html (1996).
  2. O'Neil M.J. : The Merck Index-An Encyclopedia of Chemicals, Drugs, and Biologicals (14th Edition - Version 14.9). Merck Sharp & Dohme Corp., a subsidiary of Merck & Co., Inc.. Online version available at: http://www.knovel.com/web/ portal/browse/display_EXT_KNOVEL_DISPLAY_bookid=1863&VerticalID=0 (2012).
  3. Meister R.T. and Sine C. : Farm Chemicals Handbook. Meister Publishing Company. Willoughby, Ohio, USA (1998).
  4. Roark R.C. : USDA Miscellaneous Publication No. 176. A Bibliography of Chloropicrin 1848 - 1932. United States Department of Agriculture. Washington, DC (1934).
  5. Agnihothrudu V. and Mithyantha M.S. : Pesticide Residues - a review of Indian Work. Rallis India Ltd., Bangalore (1978).
  6. US Environmental Protection Agency. Pesticide Environmental Fate One Line Summary: Chloropicrin. US EPA Environmental Fate and Effects Division. Washington, DC (1992).
  7. Shepler K, Hatton C, and Ruzo L. : Aerobic Soil Metabolism of [$^{14}C$]Chloropicrin. PTRL West Inc. Richmond, CA. (Unpublished study submitted to USEPA) (1995).
  8. Hazardous Substances Data Bank (HSDB) : Accession Number 977. National Library of Medicine, Bethesda, MD. CD ROM version: Micromedix Inc., Denver CO. (1993).
  9. Lee H. and Moreno T. : Photohydrolysis of Chloropicrin. Bolsa Research Associates. Hollister, CA. (Unpublished study submitted to USEPA) (1993).
  10. 중화인민공화국위생. 식품 중 농약 최대잔류허용량. 중국 국가표준화관리.
  11. 식품의약품안전청, 식품의약품안전청 공고 제2010-294호, 식품의 기준 및 규격 일부개정고시안 행정예고 (2010).
  12. Muir B., Carrick W.A. and Cooper D.B. : Application of central composite design in the optimisation of thermal desorption parameters for the trace level determination of the chemical warfare agent chloropicrin. Analyst 127(9), 1198-1202 (2002). https://doi.org/10.1039/b204782a
  13. OSHA. Chloropicrin Method PV2103. Salt Lake City, UT: U.S. Department of Labor, OSHA Salt Lake Technical Center (1991).
  14. Carrick WA, Cooper DB and Muir B. : Retrospective identification of chemical warfare agents by high-temperature automatic thermal desorption-gas chromatography-mass spectrometry. J. Chromatogr A 925(1-2), 241-249 (2001). https://doi.org/10.1016/S0021-9673(01)01024-X
  15. Guo M., Papiernik S.K., Zheng W. and Yates S.R. : Formation and extraction of persistent fumigant residues in soils. Environ Sci Technol ASAP Article 10.1021/es0262535 S0013-936X(02)06253-3 (2003).
  16. Castro J.A. and Godoy H. : Spectrophotometric determination of chloropicrin in water. Anal Chim Acta 33, 679-683. (1965). https://doi.org/10.1016/S0003-2670(01)84962-X
  17. US EPA. Method 551.1 : Determination of chlorinated disinfection byproducts, chlorinated solvents, and halogenated pesticides/ herbicides in drinking water by liquid/liquid extraction and gas chromatography with electron capture detection. Cincinnati, OH: U.S. EPA Office of Ground Water and Drinking Water/Technical Support Center (1995).
  18. Nikolaou A.D., Lekkas T.D., Golfinopoulos S.K. and Kostopoulou M.N. : Application of different analytical methods for determination of volatile chlorination by-products in drinking water. Talanta, 56(4), 717-726 (2002). https://doi.org/10.1016/S0039-9140(01)00613-0
  19. Kobayashi A. : Recent progress in flavor research. Nippon Shokuhin Kagaku Kogaku Kaishi, 44, 169-176 (1997). https://doi.org/10.3136/nskkk.44.169
  20. Codex Alimentarius Commission. Guidelines on good laboratory practice in residue analysis, CAC/GL 40, Rome, Italy (2003).
  21. Lee Y.D : Practical book of Korea Food Code pesticide residue analysis method. third ed. KFDA, Korea. pp. 79 (2012).

Cited by

  1. Gas Chromatographic Method for Multiresidue Analysis of Unregistered Pesticides in Imported Agricultural Commodities vol.19, pp.3, 2015, https://doi.org/10.7585/kjps.2015.19.3.161