Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/97639
標題: QuEChERS萃取技術結合液相層析串聯質譜術於蔬果中農藥殘留之分析
Analysis of Pesticide Residues in Fruits and Vegetables by Modified QuEChERS Combined with Liquid Chromatography–Tandem Mass Spectrometry
作者: 王玟心
Wen-Sin Wang
關鍵字: QuEChERS萃取技術;農藥殘留;QuEChERS;Pesticide Residues
引用: 1. 王清玲,有機農業植物保護資材規定,作物蟲害非農藥防治資材,2010,158-177. 2. 高清文,李敏郎,農藥合理化使用的現況與展望,節能減碳與作物病害管理研討會專刊,2008,87-106. 3. Robles-Molina, J.; Lara-Ortega, F. J.; Gilbert-López, B.; García-Reyes, J. F.; Molina-Díaz, A., Multi-residue method for the determination of over 400 priority and emerging pollutants in water and wastewater by solid-phase extraction and liquid chromatography-time-of-flight mass spectrometry. Journal of Chromatography A 2014, 1350, 30-43. 4. Quintana, J. B.; Rodil, R.; Muniategui-Lorenzo, S.; López-Mahía, P.; Prada-Rodríguez, D., Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry. Journal of Chromatography A 2007, 1174(1-2), 27-39. 5. Gulkowska, A.; Buerge, I. J.; Poiger, T., Online solid phase extraction LC-MS/MS method for the analysis of succinate dehydrogenase inhibitor fungicides and its applicability to surface water samples. Analytical and Bioanalytical Chemistry 2014, 406(25), 6419-6427. 6. Viñas, P.; Martínez-Castillo, N.; Campillo, N.; Hernández-Córdoba, M., Liquid-liquid microextraction methods based on ultrasound-assisted emulsification and single-drop coupled to gas chromatography-mass spectrometry for determining strobilurin and oxazole fungicides in juices and fruits. Journal of Chromatography A 2010, 1217(42), 6569-6577. 7. TSUMURA, Y.; NAKAMURA, Y.; TONOGAI, Y.; SHIBATA, T., Determination of the fungicide tecloftalam and its metabolite tecloftalam-imide in brown rice. Food Hygiene and Safety Science (Shokuhin Eiseigaku Zasshi) 1998, 39(2), 142-147_1. 8. Wick, A.; Fink, G.; Ternes, T. A., Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography–tandem mass spectrometry. Journal of Chromatography A 2010, 1217(14), 2088-2103. 9. 傅明仁,余艇,林孟山,分析樣品前處理技術,化學,1998,56(4),267-267. 10. Fritz, J.S., Analytical solid-phase extraction. 1999: Wiley-Vch. 11. Skoog, D. A.; West, D. M.; Holler, F. J.; Crouch, S., Fundamentals of analytical chemistry. 2013: Nelson Education. 12. Lee, H. B.; Weng, L. D.; Chau, A. S., Chemical derivatization analysis of pesticide residues. VIII. Analysis of 15 chlorophenols in natural water by in situ acetylation. Journal-Association of Official Analytical Chemists 1984, 67(4), 789-794. 13. Elobeid, M. A.; Almarhoon, Z. M.; Virk, P.; Hassan, Z. K.; Omer, S. A.; ElAmin, M.; Daghestani, M. H.; AlOlayan, E. M., Bisphenol A detection in various brands of drinking bottled water in Riyadh, Saudi Arabia using gas chromatography/mass spectrometer. Tropical Journal of Pharmaceutical Research 2012, 11(3), 455-459. 14. Sereshti, H.; Khosraviani, M.; Amini-Fazl, M. S., Miniaturized salting-out liquid–liquid extraction in a coupled-syringe system combined with HPLC–UV for extraction and determination of sulfanilamide. Talanta 2014, 121, 199-204. 15. Shin, J. H.; Na, Y. C.; Chung, J. H.; Gorinstein, S.; Ahn, Y. G., Quantitative analysis of heterocyclic amines in urine by liquid chromatography coupled with tandem mass spectrometry. Analytical biochemistry 2014. 447, 169-176. 16. Tran, N. H.; Hu, J.; Ong, S. L., Simultaneous determination of PPCPs, EDCs, and artificial sweeteners in environmental water samples using a single-step SPE coupled with HPLC–MS/MS and isotope dilution. Talanta 2013, 113, 82-92. 17. Wittsiepe, J.; Nestola, M.; Kohne, M.; Zinn, P.; Wilhelm, M., Determination of polychlorinated biphenyls and organochlorine pesticides in small volumes of human blood by high-throughput on-line SPE-LVI-GC-HRMS. Journal of Chromatography B 2014, 945, 217-224. 18. Möller, M.; Du Preez, J. L.; Harvey, B. H., Development and validation of a single analytical method for the determination of tryptophan, and its kynurenine metabolites in rat plasma. Journal of Chromatography B 2012, 898, 121-129. 19. Anastassiades, M.; Lehotay, S. J.; Štajnbaher, D., Quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach for the determination of pesticide residues. 2002. 20. Anastassiades, M.; Lehotay, S. J.; Štajnbaher, 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. Journal-Association of Official Analytical Chemists 2003, 86(2), 412-431. 21. Method, C. and E. 15662, Foods of Plant Origin-Determination of Pesticide Residues Using GC-MS and/or LC-MS/MS Following Acetonitrile Extraction/Partitioning and Cleanup by Dispersive SPE-QuEChERS-Method. 2008, European Committee for Standardization. 22. 李仁傑,王培成,李茂榮,新前處理技術-QuEChERS 之簡介,科儀新知,2011,183,67-74. 23. Kiljanek, T.; Niewiadowska, A.; Semeniuk, S.; Gaweł, M.; Borzęcka, M.; Posyniak, A., Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry-Honeybee poisoning incidents. Journal of Chromatography A 2016, 1435, 100-114. 24. Chawla, S.; Patel, H. K.; Vaghela, K. M.; Pathan, F. K.; Gor, H. N.; Patel, A. R.; Shah, P. G., Development and validation of multiresidue analytical method in cotton and groundnut oil for 87 pesticides using low temperature and dispersive cleanup on gas chromatography and liquid chromatography-tandem mass spectrometry. Analytical and Bioanalytical Chemistry 2016, 408(3), 983-997. 25. Cunha, S. C.; Fernandes, J. O., Development and validation of a method based on a QuEChERS procedure and heart‐cutting GC‐MS for determination of five mycotoxins in cereal products. Journal of separation science 2010, 33(4‐5), 600-609. 26. Koesukwiwat, U.; Sanguankaew, K.; Leepipatpiboon, N., Rapid determination of phenoxy acid residues in rice by modified QuEChERS extraction and liquid chromatography–tandem mass spectrometry. Analytica chimica acta 2008, 626(1), 10-20. 27. Kmellár, B.; Fodor, P.; Pareja, L.; Ferrer, C.; Martínez-Uroz, M. A.; Valverde, A.; Fernandez-Alba, A. R., Validation and uncertainty study of a comprehensive list of 160 pesticide residues in multi-class vegetables by liquid chromatography–tandem mass spectrometry. Journal of Chromatography A 2008, 1215(1-2), 37-50. 28. de Hoffmann, E.; Stroobant, V., Mass Spectrometry: Principles and Applications. 2007: John Wiley & Sons. 29. Yost, R. A.; Enke, C. G., Triple quadrupole mass spectrometry for direct mixture analysis and structure elucidation. Analytical chemistry 1979, 51(12), 1251-1264. 30. Johnson, J. V.; Yost, R. A.; Kelley, P. E.; Bradford, D. C., Tandem-in-space and tandem-in-time mass spectrometry: triple quadrupoles and quadrupole ion traps. Analytical Chemistry 1990, 62(20), 2162-2172. 31. Skoog, D. A.; Holler, F. J.; Crouch, S. R. Principles of instrumental analysis. 2017: Cengage learning. 32. Yamashita, M.; Fenn, J. B., Electrospray ion source. Another variation on the free-jet theme. The Journal of Physical Chemistry 1984, 88(20), 4451-4459. 33. Henderson, W.; Nickleson, B. K.; McCaffrey, L. J., Applications of electrospray mass spectrometry inorganometallic chemistry. Polyhedron 1998, 25(17), 4291-4313. 34. Dole, M.; Mack, L. L.; Hines, R. L.; Mobley, R. C.; Ferguson, L. D.; Alice, M. B., Molecular beams of macroions. The Journal of Chemical Physics 1968, 49(5), 2240-2249. 35. Iribarne, J. V.; Thomson, B. A., On the evaporation of small ions from charged droplets. The Journal of Chemical Physics 1976, 64(6), 2287-2294. 36. Dass, C., Fundamentals of contemporary mass spectrometry. Vol. 16. 2007: John Wiley & Sons. 37. Konermann, L.; Ahadi, E.; Rodriguez, A. D.; Vahidi, S., Unraveling the mechanism of electrospray ionization. Analytical Chemistry 2013, 85, 2-9. 38. Fersht, A., Structure and mechanism in protein science: a guide to enzyme catalysis and protein folding. 1999: Macmillan. 39. Ahadi, E.; Konermann, L., Modeling the behavior of coarse-grained polymer chains in charged water droplets: implications for the mechanism of electrospray ionization. The Journal of Physical Chemistry B 2011, 116(1), 104-112. 40. Konermann, L.; Rodriguez, A. D.; Liu, J., On the formation of highly charged gaseous ions from unfolded proteins by electrospray ionization. Analytical chemistry 2012, 84(15), 6798-6804. 41. Creighton, T.E., Proteins: structures and molecular properties. 1993: Macmillan. 42. Jiang, Z.; Li, H.; Cao, X.; Du, P.; Shao, H.; Jin, F.; Jin, M.; Wang, J., Determination of hymexazol in 26 foods of plant origin by modified QuEChERS method and liquid chromatography tandem-mass spectrometry. Food chemistry 2017, 228, 411-419.
摘要: 
本研究發展快速 (Quick)、簡單 (Easy)、便宜 (Cheap)、有效 (Effective)、耐用 (Rugged) 及安全 (Safe) 之 QuEChERS 萃取技術結合液相層析串聯質譜術 (Liquid Chromatography-Tandem Mass Spectrometry) 於蔬果中 Diafenthiuron、Dicamba、Fenpyrazamine、Hymexazol、Thiocyclam、Tridemorph 及 Tecloftalam 等七種殘留農藥進行檢測。
  實驗結果之 QuEChERS 方法最佳化條件,於離心管中加入 2 g 均質化之蔬果樣品,添加 2 mL 含 1% 醋酸之乙腈溶劑進行液液萃取,渦流震盪 1 分鐘並靜置 10 分鐘後,加入 800 mg 無水硫酸鎂及 200 mg 無水醋酸鈉,蓋上離心管蓋後隨即震盪數次以防鹽類結塊,接著渦流震盪 1 分鐘並以 3000 rpm 離心 5 分鐘後,取上清液 1.2 mL 置於含 80 mg florisil 及 180 mg 無水硫酸鎂的離心管中,渦流震盪 1 分鐘並以 3000 rpm 離心 5 分鐘後,取上清液 0.6 mL,並以氮氣吹乾後加入 200 μL 初始動相溶液進行回溶,通過 0.22 μm PVDF 濾膜後,取得之溶液以 LC-MS/MS 進行上機分析。於此條件下,偵測蔬果樣品中七種農藥之線性範圍為 0.1-1000 ng/g,線性相關係數 (R2) 均在 0.9977 以上,偵測極限介於 0.03-0.12 ng/g。本研究不僅可以有效地降低有機溶劑之使用量,減少樣品前處理時間,具有高靈敏度並可應用於其他蔬果中殘留農藥之分析。

In this study, the QuEChERS (quick, easy, cheap, effective, rugged, and safe) as sample preparation method and combined with liquid chromatography/tandem mass spectrometry (LC-MS/MS) was proposed to determine seven pesticides including diafenthiuron, dicamba, fenpyrazamine, hymexazol, thiocyclam, tridemorph, and tecloftalam in fruits and vegetables.
  The extraction efficiency of QuEChERS were systematically studied and the optimal extraction conditions were as follow:2 g of homogenized fruits or vegetables were extracted with 2 mL of acetonitrile containing 1% acetic acid. Then the sample was vortexed for 1 min and left for 10 min. For phase separation, 800 mg anhydrous magnesium sulfate and 200 mg sodium acetate anhydrous were added. The tube was immediately shaken to avoid the caking behavior of salt, vortexed in a Vortex-Mixer for 1 min, and then centrifuged for 5 min at 3000 rpm. A 1.2 mL aliquot of the supernatant was transferred to a centrifuge tube containing 180 mg anhydrous magnesium sulfate and 80 mg florisil. The tube was vortexed for 1 min and centrifuged at 3000 rpm for 5 min. A 0.6 mL of the resulting supernatant was evaporated to dryness under a stream of nitrogen, and reconstituted using 200 μL of initial mobile phase. Finally, the extract was filtered through 0.22 μm PVDF syringe filter and then placed into a glass autosampler vial for LC-MS/MS analysis. In this study, the linear range for seven pesticides was from 0.1 to 1000 ng/g with coefficients of determination (R2) above 0.9977. The limits of detection (LODs) of proposed method ranged from 0.03 to 0.12 ng/g. The results showed the developed method can efficiently decrease the usage of organic solvent, reduce the operation time, and successfully utilized for analyzing of trace pesticides in fruits or vegetables.
URI: http://hdl.handle.net/11455/97639
Rights: 同意授權瀏覽/列印電子全文服務,2018-08-30起公開。
Appears in Collections:化學系所

Files in This Item:
File SizeFormat Existing users please Login
nchu-107-7105051022-1.pdf3.85 MBAdobe PDFThis file is only available in the university internal network    Request a copy
Show full item record
 

Google ScholarTM

Check


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.