Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

The Korean Society of Food Hygiene and Safety (한국식품위생안전성학회)
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Improvement of an Analytical Method for Fluoroimide Residue in Agricultural Products Using LC-MS/MS

LC-MS/MS를 이용한 농산물 중 Fluoroimide의 잔류농약 분석법 개선

  • Kim, Nam Young (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Park, Eun-Ji (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Shim, Jae-Han (Division of Applied Bioscience and Biotechnology College of Agriculture and Life Sciences, Chonnam National University) ;
  • Lee, Jung Mi (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Jung, Yong Hyun (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Oh, Jae-Ho (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 김남영 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 박은지 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 심재한 (전남대학교 농업생명과학대학 농식품생명화학부) ;
  • 이정미 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 정용현 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 오재호 (식품의약품안전처 식품의약품안전평가원 잔류물질과)
  • Received : 2021.02.04
  • Accepted : 2021.05.24
  • Published : 2021.06.30
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Abstract

Fluoroimide is a fungicide and is also used as a pesticide for persimmons and potatoes. The established fluoroimide pesticide analysis method takes a long time to perform and uses benzene, a carcinogen. In addition, a lower limit of quantification is required due to enforcement of the Positive List System. Therefore, this study aimed to improve the analysis method for residual fluoroimide to resolve the problems associated with the current method. The analytical method was improved with reference to the increased stability of fluoroimide under acidic conditions. Fluoroimide was extracted under acidic conditions by hydrogen chloride (4 N) and acetic acid. MgSO4 and NaCl were used with acetonitrile. C18 (octadecylsilane) 500 mg and graphitized carbon black 40 mg were used in the purification process. The experiment was conducted with agricultural products (hulled rice, potato, soybean, mandarin, green pepper), and liquid chromatograph-tandem mass spectrometry was used for the instrumental analysis. Recovery of fluoroimide was 85.7-106.9% with relative standard deviations (RSDs) of less than 15.6%. This study reports an improved method for the analysis of fluoroimide that might contribute to safety by substituting the use of benzene, a harmful solvent. Furthermore, the use of QuEChERS increased the efficiency of the improved method. Finally, this research confirmed the precise limit of quantification and these results could be used to improve the analysis of other residual pesticides in agricultural products.

Fluoroimide는 감과 감자의 둥근무늬낙엽병과 역병을 억제하는데 효과가있는 살진균제로서, 이전 사용되었던 fluoroimide의 시험법은 전처리시 발암물질인 benzene을 사용하는 문제가 있었으며, 복잡한 시험법으로 인해 시간이 오래걸리고 효율이 떨어지는 단점이 있었다. 또한, fluoroimide의 특성상 산성에서 안정한 편이므로 전처리 시 이를 고려해야 하는 문제가 있었으며, PLS시행에 따라 기존의 정량한계인 0.05 mg/kg보다 낮은 정량한계 요구로 인해 fluoroimide에 대한 새로운 전처리방법이 필요하였다. Fluoroimide가 산성에서 안정한 특성을 고려하여, 추출 시 4N의 염산을 사용하였고 용매는 acetic acid가 포함된 acetonitrile을 사용하였으며, MgSO4와 NaCl을 통해 추출하였다. 정제는 C18 (Octadecylsilane)과 GCB (graphitized carbon black)를 첨가하여 정제하였으며, 기기분석은 LC-MS/MS로 분석하였다. 대표농산물 5종(현미, 감자, 대두, 감귤, 고추)을 대상으로 정량한계(0.01 mg/kg), 정량한계 10배(0.1 mg/kg), 정량한계 50배(0.5 mg/kg)의 수준으로 회수율 실험을 5반복 실시하였으며, 그 결과는 농산물 5종에서 85.7-106.9%의 회수율을 확인하였으며, 분석오차는 15.6% 이하의 결과를 보여, 국제식품 규격위원회 가이드라인의 잔류농약 분석 기준 및 '식품등 시험법 마련 표준절차에 관한 가이드라인(2016)'에 부합하였다. 상기의 결과를 통해 개선한 fluoroimide의 시험법은 benzene을 대체해 실험자의 안전성을 확보하였고, QuEChERS법을 적용하여 효율을 높여, 안전관리에 대한 공정시험법으로서 활용가능할 것으로 사료된다.

Keywords

Acknowledgement

This study was supported by a grant (19161수안기582) of MINISTRY OF FOOD AND DRUG SAFETY in 2019, Republic of KOREA.

References

  1. Paranjape, K., Gowariker, V., Krishnamurthy, V.N., Gowariker, S., 2014. The pesticide encyclopedia. CABI, Walling ford, Oxfordshire, UK, pp. 215.
  2. National Institute of Food and Drug Safety Evaluation, 2020. Pesticides MRLs in agricultural commodities. National Institute of Food and Drug Safety Evaluation, Cheongju, Korea, pp. 157.
  3. Mamun, I.R., Park, J.H., Choi, J.H., Kim, H.K., Choi, W.J., Han, S.S., Hwang, K.S., Jang, N.I., Assayed, M.E., El-dib, M.A., Shin, H.C., El-aty, A.M.A., Shim, J.H., Development and validation of a multiresidue method for determination of 82 pesticides in water using GC. J. Sep. Sci., 32, 559-574 (2009). https://doi.org/10.1002/jssc.200800606
  4. Kim, M.J., Jung, S.S., Park, J.S., Kim, J.E., Lee, Y.D., Kim, J.H., Oh, C.H., Application of the pesticide multiresidue analysis method for potatoes and carrots. Korean J. Food Sci. Technol., 37, 304-307 (2005).
  5. Ock, H.S., Developmental trend of analytical methods for pesticide residues. Korean J. Pest. Sci., 13, 336-348 (2009).
  6. Cha, C.H., Kim, K.J., Kim, J.C., Paik, N.W., Development of technology for environmental assessment and biological monitoring of workers exposed to benzene. Korean J. Occup. Environ. Med., 6, 122-133 (1994). https://doi.org/10.35371/kjoem.1994.6.1.122
  7. An, S.C., Kang, J.W., Kim, H., Effects of benzene exposure on genetic damage of human white blood cells. Chungbuk Med. J., 13, 189-204 (2003).
  8. Blair, A., Marrett, L., Beane Freeman, L., Occupational cancer in developed countries. Environ. Health, 10(suppl 1), S9 (2011). https://doi.org/10.1186/1476-069X-10-S1-S9
  9. Baek, K., Park, D., Ha, K., Benzene exposure matrices using employee's exposure assessment data. J. Korean Soc. Occup. Environ. Hyg., 25, 146-155 (2015). https://doi.org/10.15269/JKSOEH.2015.25.2.146
  10. Hwang, I.G., Moon, G.I., Jang, M.I., Kim, S.H., Ko, Y.H., Jo, Y.J., Lee, S.M., Kang, Y.W., Heo, E.J., Im, H.S., Seo, I.W., Kang, T.S., 2016. Guideline on standard procedures for preparing analysis method. Ministry of Food and Drug Safety, Cheongju, Korea, pp. 2-16.
  11. Anastassiades, M., Lehotay, S.J., Stajnbaher, D., Schenck, F.J., 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, 412-431 (2003). https://doi.org/10.1093/jaoac/86.2.412
  12. CODEX Alimentarius Commission, (2021, May 28). Guidelines on good laboratory practice in residue analysis (2003, CAC/GL 40-1993). Retrieved from https://products.ihs.com/Ohsis-SEO/779086.html
  13. Wilkowska, A., Biziuk, M., Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chem., 125, 803-812 (2011). https://doi.org/10.1016/j.foodchem.2010.09.094
  14. Rejczak, T., Tuzimski, T., A review of recent developments and trends in the QuEChERS sample preparation approach. Open Chem., 13, 980-1010 (2015).
  15. Lee, S.J., Lee, G.S., Jang, M.I., Lee, S.M., Kim, H.J., Kim, M.K., Jo, Y.J., Kim, M.A., Lee, Y.D., 2017. Food code residue pesticide manual, fifth ed. Ministry of Food and Drug Safety, Cheongju, Korea, pp. 610-612.