Korean Journal of Food Science and Technology (한국식품과학회지)

Korean Society of Food Science and Technology (한국식품과학회)
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Establishment of an Analytical Method for Prometryn Residues in Clam Using GC-MS

GC-MS를 이용한 바지락 중 prometryn 잔류분석법 확립

  • Chae, Young-Sik (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Cho, Yoon-Jae (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Jang, Kyung-Joo (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, Jae-Young (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Lee, Sang-Mok (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Chang, Moon-Ik (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 채영식 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 조윤제 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 장경주 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 김재영 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이상목 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 장문익 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2013.03.18
  • Accepted : 2013.07.30
  • Published : 2013.10.31
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Abstract

We developed a simple, sensitive, and specific analytical method for prometryn using gas chromatography-mass spectrometry (GC-MS). Prometryn is a selective herbicide used for the control of annual grasses and broadleaf weeds in cotton and celery crops. On the basis of high specificity, sensitivity, and reproducibility, combined with simple analytical operation, we propose that our newly developed method is suitable for use as a Ministry of Food and Drug Safety (MFDS, Korea) official method in the routine analysis of individual pesticide residues. Further, the method is applicable in clams. The separation condition for GC-MS was optimized by using a DB-5MS capillary column ($30m{\times}0.25mm$, 0.25 ${\mu}m$) with helium as the carrier gas, at a flow rate of 0.9 mL/min. We achieved high linearity over the concentration range 0.02-0.5 mg/L (correlation coefficient, $r^2$ >0.998). Our method is specific and sensitive, and has a quantitation limit of 0.04 mg/kg. The average recovery in clams ranged from 84.0% to 98.0%. The reproducibility of measurements expressed as the coefficient of variation (CV%) ranged from 3.0% to 7.1%. Our analytical procedure showed high accuracy and acceptable sensitivity regarding the analytical requirements for prometryn in fishery products. Finally, we successfully applied our method to the determination of residue levels in fishery products, and showed that none of the analyzed samples contained detectable amounts of residues.

Prometryn은 트리아진계 제초제로 일년생 쌍자엽 식물체와 같은 일년생 잡초 제거에 탁월한 효과가 있으나 일부 토양에 약효가 여러 달 지속될 경우 수중계에 스며들어 축적과 이동, 생물학적 농축(biomagnification)등의 심각한 환경문제를 비롯한 수질오염, 야생동물 및 국민건강에 심각한 문제를 일으킬 수 있는 잔류물질이다. 최근 국내에서 중국산 바지락 및 그 가공품에서 prometryn의 검출이 보고된 바 있어 이에 대한 지속적인 모니터링이 필요하기 때문에 바지락 중의 prometryn 분석법 개발이 필요한 실정이다. 본 연구에서는 수산물 중 바지락을 시료로 사용하였다. 시료를 아세토니트릴로 추출하고 농축한 다음 20% 아세톤 함유 헥산을 첨가하여 용해하였다. 이 용액을 florisil 카트리지로 정제한 후 농축하여 GC-MS로 분석하였다. 기기분석은 SIM 모드로 m/z 241 이온에 대하여 정량하였고, LOQ는 0.04 mg/kg으로 계산되었으며, LOQ, $2{\times}LOQ$ 농도에서의 회수율 및 분석오차가 각각 84.0-98.0%, 3.1-7.1%로 분석되어 Codex 가이드라인 규정에 만족하였다.

Keywords

References

  1. Kim JH. Pesticide and its importance. Vol. 2, pp 48-52. In: Safe Food Forum. The Korean Society of Food Hygiene and Safety, Seoul, Korea (2007)
  2. Lang DH, Rettie AE, Bocker RH. Identification of enzymes involved in the metabolism of atrazine, terbuthylazine, ametryne, and terbutryne in human liver microsomes. Chem. Res. Toxicol. 10: 1037-1044 (1997) https://doi.org/10.1021/tx970081l
  3. Brvar M, Okrajsek R, Kosmina P, Staric F, Keps R, Kozelj G, Bunc M. Metabolic acidosis in prometryn (triazine herbicide) self-poisoning. Clin. Toxicol. 46: 270-273 (2008) https://doi.org/10.1080/15563650701665126
  4. Navarro S, Vela N, Gimenez MJ, Navarro G. Persistence of four s-triazine herbicides in river, sea and groundwater samples exposed to sunlight and darkness under laboratory conditions. Sci. Total Environ. 329: 87-97 (2004) https://doi.org/10.1016/j.scitotenv.2004.03.013
  5. Sabik H, Jeannot R, Rondeau B. Multiresidue methods using solid-phase extraction techniques for monitoring priority pesticides, including triazines and degradation products, in ground and surface waters. J. Chromatogr. A 885: 217-236 (2000) https://doi.org/10.1016/S0021-9673(99)01084-5
  6. Dean JR, Wade G, Barnabas IJ. Determination of triazine herbicides in environmental samples. J. Chromatogr. A 733: 295-335 (1996) https://doi.org/10.1016/0021-9673(95)00691-5
  7. Sanchez-Ortega A, Unceta N, Gomez-Caballero A, Sampedro MC, Akesolo U, Goicolea MA, Barrio RJ. Sensitive determination of trianines in underground waters using stir bar sorptive extraction directly coupled to automated thermal desorption and gas chromatography-mass spectrometry. Anal. Chim. Acta 641: 110-116 (2009) https://doi.org/10.1016/j.aca.2009.03.044
  8. EPA. Reregistration eligibility decision (RED) prometryn. U.S. Environmental Protection Agency, Washington, DC, USA (1996)
  9. Chunhong Z, Yun L, Wei Y, Xiaogang C, Zhengxing C. Simultaneous determination of residues of triazine herbicides in wheat by ultra performance LCTM. Mod. Sci. Instrum. 4: 70-73 (2007)
  10. MFDS. Food code. Ministry of Food and Drug Safety, Cheongwon, Korea. pp. appendix.4.52. (2012)
  11. MFDS. Food code. Ministry of Food and Drug Safety, Cheongwon, Korea. pp. 10.4.478-483 (2012)
  12. MFDS. Food code. Ministry of Food and Drug Safety, Cheongwon, Korea. pp. 10.4.2-10 (2012)
  13. Oh JH, Kwon CH, Jeon JS, Choi DM. Management of veterinary drug residues in food. Korean J. Environ. Agric. 28: 310-325 (2009) https://doi.org/10.5338/KJEA.2009.28.3.310
  14. Codex. Codex Guidelines for the Establishment of a Regulatory Programme for Control of Veterinary Drug Residues in Foods, CAC/GL 16. Codex Alimentarius Commission, Roma, Italy (1993)
  15. AOAC. Official Method of Analysis of AOAC Intl. 18th ed. Method 2007.01. Association of Official Analytical Communities, Arlington, VA, USA (2010)
  16. U.S. FDA. Pesticide analytical manual, Vol 1: Multi-residue method, 3rd ed. U.S. Food and Drug Administration, Silverspring, MD, USA (1999)
  17. Lee YD. Manual of analytical method for residue pesticide on Korean food standards codex. Ministry of Food and Drug Safety, Cheongwon, Korea. pp. 11-25 (2012)