Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

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

DOI QR Code

Investigation on Pesticide Residues in Agricultural Products in Domestic Markets Using LC-MS/MS and GC-MS/MS

LC-MS/MS 및 GC-MS/MS를 이용한 국내 유통 농산물 중 잔류농약 실태조사

  • Ji-Yeon Bae (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Da-Young Yun (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Nam Suk Kang (Center for Food and Drug Analysis, Busan Regional Office of Food and Drug Safety, MFDS) ;
  • Won Jo Choe (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Yong-Hyeon Jeong (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Gui Hyun Jang (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Guiim Moon (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 배지연 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 윤다영 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 강남숙 (식품의약품안전처 부산지방식품의약품안전청 시험분석센터) ;
  • 최원조 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 정용현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 장귀현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 문귀임 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2023.03.24
  • Accepted : 2023.04.26
  • Published : 2023.06.30
Download PDF
⟨ Previous Next ⟩

Abstract

In this study, we investigated pesticide residue levels in 535 domestically distributed agricultural products in South Korea using multi-residue analysis. Agricultural products from 13 regions, including Seoul, were pretreated using QuEChERS and d-SPE, and subsequently analyzed using LC-MS/MS and GC-MS/MS. Residual pesticides were detected in 288 (53.8%) out of the 535 samples, including 40 of apples, 40 of peppers, 33 of mandarins, 31 of peaches, and 144 other commodities. Furthermore, one sample of Korean cabbage exceeded the permitted maximum residue limit (MRL), diniconazole (0.18 mg/kg), detected at about twice the MRL. In total, 91 types of residual pesticides were detected, including fungicides (42), insecticides (48), and a nematicide. The most frequently detected pesticides were dinotefuran (91), carbendazim (75), tebuconazole (61), and pyraclostrobin (59). Our results showed that continuous monitoring of agricultural products is necessary.

본 연구는 국내 유통 농산물 535건을 대상으로 잔류농약 실태조사를 수행하였다. 서울 등 13개 지역에서 수거한 농산물 시료를 QuEChERS법으로 추출한 후 d-SPE로 정제하여 LC-MS/MS 및 GC-MS/MS로 분석하였다. 농산물 15품목 535건 중 14품목 288건에서 잔류농약이 검출(53.8%)되었으며, 검출된 농산물은 사과 40건, 고추 40건, 감귤 33건, 복숭아 31건, 기타 품목 144건이었다. 이 중 잔류허용기준을 초과한 농산물은 배추 1건으로, diniconazole이 0.18 mg/kg으로 기준치의 약 2배 검출되었다. 총 검출된 농약은 91종으로 살균제 42종, 살충제 48종, 살선충제 1종이었으며, dinotefuran 91건, carbendazim 75건, tebuconazole 61건, pyraclostrobin 59건이 가장 빈번하게 검출되었다. 따라서 상기의 결과를 통해 과일류 및 채소류에 대한 지속적인 잔류실태조사가 필요할 것으로 사료된다.

Keywords

Acknowledgement

본 연구는 2021년도 식품의약품안전평가원 "신규 시험법 대상 농약에 대한 농산물 중 잔류실태 조사(21161농축산363)"의 연구개발비 지원에 의해 수행되었으며, 이에 감사드립니다.

References

  1. Yu, J.S., Lim, T.H., Lee, D.W., Status of registered fungicides and insecticides by toxicity, formulation and classification in Korea since 1980s. Korean J. Pestic. Sci., 24, 19-33 (2020). https://doi.org/10.7585/kjps.2020.24.1.19
  2. Yoo, N.Y., Kim, K.Y., Kim, Y.S., Kim, S.T., Song, S.H., Lim, J.H., Han, Y.L., Choi, H.J., Kim, Y.H., Seo, J.H., Choi, O.K., Analysis of pesticide residues in stalk and stem vegetables marketed in northern Gyeonggi-do. J. Food Hyg. Saf., 37, 149-158 (2022). https://doi.org/10.13103/JFHS.2022.37.3.149
  3. Bae, C.H., Cho, K.W., Kim, Y.S., Park, H.J., Shin, K.S., Park, Y.K., Lee, K.S., Honeybee toxicity by residues on tomato foliage of systemic insecticides applied to the soil. Korean J. Pesti. Sci., 17,178-184 (2013). https://doi.org/10.7585/kjps.2013.17.3.178
  4. Kim, J.Y., Lee, S.M., Lee, H.J., Chang, M.I., Kang, N.S., Kim, N.S., Kim, H.J., Cho, Y.J., Jeong, J.Y., Kim, M.K., Rhee, G.S., Monitoring and risk assessment of pesticide residues for circulated agricultural commodities in Korea-2013. J. Appl. Biol. Chem., 57, 235-242 (2014). https://doi.org/10.3839/jabc.2014.037
  5. Park, B.K., Jung, S.H., Kwon, S.H., Ye, E.Y., Lee, H.J., Seo, S.J., Joo, K.S., Heo, M.J., Monitoring and risk assessment of pesticide residues on stalk and stem vegetables marketed in Incheon metropolitan area. J. Food Hyg. Saf., 35, 365-374 (2020). https://doi.org/10.13103/JFHS.2020.35.4.365
  6. Chung, S.J., Kim, H.Y., Kim, J.H., Yeom, M.S., Cho, J.H., Lee, S.Y., Monitoring of pesticide residues and risk assessment in some fruits on the market in Incheon. Korean J. Environ. Agric., 33, 111-120 (2014). https://doi.org/10.5338/KJEA.2014.33.2.111
  7. Do, J.A., Lee, H.J., Shin, Y.W., Choe, W.J., Chae, K.R., Kang, C.S., Kim, W.S., Monitoring of pesticide residues in domestic agricultural products. J. Korean Soc. Food Sci. Nutr., 39, 902-908
  8. Ministry of Food and Drug Safety, (2023, March 20). Food Code. Retrieved from https://www.mfds.go.kr/brd/m_211/view.do?seq=14626&srchFr=&srchTo=&srchWord=&srchTp=&itm_seq_1=0&itm_seq_2=0&multi_itm_seq=0&company_cd=&company_nm=&page=1
  9. Ministry of Food and Drug Safety, (2023, March 20). Pesticides MRLs in agricultural commodities. Retrieved from https://various.foodsafetykorea.go.kr/fsd/#/ext/Document/FC
  10. Codex Alimentarius Commission, (2023, March 20) Guidelines on standard procedures for preparing analysis method. Retrieved from https://www.fao.org/fao-who-codexalimentarius/sh-proxy/en/?lnk=1&url=https%253A%252F%252Fworkspace.fao.org%252Fsites%252Fcodex%252FStandards%252FCXG%2B40-1993%252Fcxg_040e.pdf
  11. Ministry of Food and Drug Safety, (2023, March 20). Guidelines on standard procedures for preparing analysis method. Retrieved from https://www.mfds.go.kr/brd/m_1060/view.do?seq=12920&srchFr=&srchTo=&srchWord=&srchTp=&itm_seq_1=0&itm_seq_2=0&multi_itm_seq=0&company_cd=&company_nm=&page=69
  12. Ministry of Food and Drug Safety, 2017. Analytical practices manual for pesticide residues in foods. 5th edition, Ministry of food and drug safety, Cheong ju, Korea, pp. 78-79.
  13. Kang, N.S., Kim, S.C., Kang, Y.J., Kim, D.H., Jang, J.W., Won, S.R. Hyun, J.H., Kim, D.E., Jung, I.Y., Rhee, G.S., Shin, Y.M., Joung, D.Y., Kim, S.Y., Park, J.Y., Kwon, K.S., Ji, Y.A., Monitoring and exposure assessment of pesticide residues in domestic agricultural products. Korean J. Pesti. Sci., 19, 32-40 (2015). https://doi.org/10.7585/kjps.2015.19.1.32
  14. Park, B.K., Kwon, S.H., Yeom, M.S., Han, S.Y., Kang, M.J., Seo, S.J., Joo, K.S., Heo, M.J., Monitoring and risk assessment of pesticide residues in school foodservice agricultural products in Incheon. Korean J. Food Sci. Technol., 53, 470-478 (2021).
  15. Jeong, J.Y., Sung, G.H., Cho, H.N., Jung, M.G., Lee, S.Y., Park, S.W., Kim, B.J., A survey on pesticide residues in agricultural products for Juice on the market in Busan. The Annual Report of Busan Metropolitan City Institute of Health & Environment, 31, 329-338 (2022).
  16. Lee, K.B., Kim, N.W., Song, N.S., Lee, J.H., Jung, S.M., Shin, M.H., Choi, S.S., Kim, J.H., Sung, S.Y., A safety survey of pesticide residues in fruit products circulated in Chungcheongnam-do Province. Korea. J. Food Hyg. Saf., 34, 421-430 (2019). https://doi.org/10.13103/JFHS.2019.34.5.421
  17. Choi, S.J., Kim, E.J., Lee, J.I., Cho, I.S., Park, W.H., Hwang, I.S., Kim, M.S., Kim, G.H., Determination of post-harvest fungicide in citrus fruits using LC-MS. Korean J. Food Sci. Technol., 45, 409-415 (2013). https://doi.org/10.9721/KJFST.2013.45.4.409
  18. Lee, H.D., Kyung, K.S., Kwon, H.Y., Ihm, Y.B., Kim, J.B., Park, S.S., Kim, J.E. Residue characteristics of hexaconazole and chlorothalonil in several fruits. Korean J. Pesti. Sci., 8, 107-111 (2004).
  19. Kim, H.J., Cho, H.C., Lee, J.H., Ku, P.T., Na, Y.R., Lee, I.S., Kim, K.A, Hwang, I.Y., Kim, C.H., A study on the pesticide residues of circulating pepper powder in Busan area (2010). The Annual Report of Busan Metropolitan City Institute of Health & Environment, 20, 62-66 (2010).
  20. Yang, Y.S., Gang, G.R., Lee, S.M., Kim, S.G., Lee, M.G., Choi, E.N., Seo, K.W., Kim, E.S., Kim, J.H., Survey on pesticide residues and risk assessment of agricultural products from wholesale market in Gwangju (2014-2016). Korean J. Pesti. Sci., 21, 341-354 (2017). https://doi.org/10.7585/kjps.2017.21.4.341
  21. Ryu, K.Y., Kim, J.P., Park, D.W., Lee, D.V., Song, N.J., Cho, B.S., Seo, K.W., Kim, S.H., A statistical analysis of pesticide residues on leafy vegetables selling at agricultural wholesale markets in Gwangju. Korean J. Pesti. Sci., 24, 91-104 (2020). https://doi.org/10.7585/kjps.2020.24.1.91
  22. Pang, S., Lin, Z., Zhang, W., Mishra, S., Bhatt, P., Chen, S., Insights into the microbial degradation and biochemical mechanisms of neonicotinoids. Front. Microbiol., 11 (2020).
  23. Vela-Corcia, D., Romero, D., de Vicente, A., Perez-Garcia, A., Analysis of β-tubulin-carbendazim interaction reveals that binding site for MBC fungicides does not include residues involved in fungicide resistance. Sci. Rep., 8 (2018).
  24. Bhattacherjee, A.K., Pandey, B.K., Dissipation of carbendazim in mango after pre- and post-harvest treatments. J. Plant Protect. Sci., 2, 65-70 (2010).
  25. Medina, A., Mateo, R., Valle-Algarra, F.M., Mateo, E.M., Jimenez, M., Effect of carbendazim and physicochemical factors on the growth and ochratoxin A production of Aspergillus carbonarius isolated from grapes. Int. J. Food Microbiol., 119, 230-235 (2007). https://doi.org/10.1016/j.ijfoodmicro.2007.07.053
  26. Sehnem, Nicole T., Souza-Cruz, P., Peralba, Maria Do Carmo R., Ayub, Marco A. Zachia, Biodegradation of tebuconazole by bacteria isolated from contaminated soils. J. Environ. Sci. Health B, 45, 67-72 (2010).
  27. Dubey, J.K., Patyal, S.K., Katna, S., Shandil, D., Devi, N., Singh, G., Singh, G., Persistence and dissipation kinetics of tebuconazole in apple, tomato, chilli and onion crops of Himachal Pradesh, India. Environ. Sci. Pollut. Res. Int., 27, 11290-11302 (2020). https://doi.org/10.1007/s11356-020-07724-5
  28. Wijntjes, C., Weber, Y., Hoger, S., Nguyen, K.T., Hollert, H., Schaffer, A., Decelerated degradation of a sulfonylurea herbicide in four fungicide-treated soils. Environ. Sci.: Adv., 1, 70-82 (2022). https://doi.org/10.1039/D1VA00021G
  29. Yin, Y.N., Kim, Y.K., Xiao, C.L., Molecular characterization of pyraclostrobin resistance and structural diversity of the cytochrome b Gene in botrytis cinerea from apple. Phytopathology, 102, 315-322 (2012). https://doi.org/10.1094/PHYTO-08-11-0234
  30. Gao, Y., Yang, S., Li, X., He, L., Zhu, J., Mu, W., Liu, F., Residue determination of pyraclostrobin, picoxystrobin and its metabolite in pepper fruit via UPLC-MS/MS under open field conditions. Ecotoxicol. Environ. Saf., 182, 109445 (2019).