Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/14279
標題: QuEChERS 結合氣相層析質譜術於乳酸飲料中苯乙烯與苯乙酮及塑化劑之研究
Determination of Styrene, Acetophenone and Phthalates in Beverages by QuEChERS Combined with Gas Chromatography-Mass Spectrometry
作者: 陳雅瑩
Chen, Ya-Ying
關鍵字: 苯乙烯;QuEChERS;苯乙酮;塑化劑;氣相層析質譜;styrene;acetophenone;phthalates;GC-MS
出版社: 化學系所
引用: 伍、參考文獻 1. Hueber-Becker, F., Nohynek, G.J., Meuling, W.J.A., Benech-Kieffer, F. & Toutain, H. Human systemic exposure to a [C-14]-para-phenylenediamine-containing oxidative hair dye and correlation with in vitro percutaneous absorption in human or pig skin. Food Chem Toxicol 42, 1227-1236 (2004). 2. Sardas, S., Aygun, N. & Karakaya, A.E. Genotoxicity studies on professional hair colorists exposed to oxidation hair dyes. Mutat Res-Gen Tox En 394, 153-161 (1997). 3. Miller, M.E. & Stuart, J.D. Comparison of gas-sampled and SPME-Sampled static headspace for the determination of volatile flavor components. Anal Chem 71, 23-27 (1999). 4. Kusch, P. & Knupp, G. Analysis of residual styrene monomer and other volatile organic compounds in expanded polystyrene by headspace solid-phase microextraction followed by gas chromatography and gas chromatography/mass spectrometry. J Sep Sci 25, 539-542 (2002). 5. Karlsson, S. Recycled polyolefins. Material properties and means for quality determination. Adv Polym Sci 169, 201-229 (2004). 6. Vilaplana, F. & Karlsson, S. Quality concepts for the improved use of recycled polymeric materials: A review. Macromol Mater Eng 293, 274-297 (2008). 7. Schmitt, H. Baubedarf Manager, 1-6 (1985). 8. Kamarei, F., Ebrahimzadeh, H. & Yamini, Y. Optimization of ultrasound-assisted emulsification microextraction with solidification of floating organic droplet followed by high performance liquid chromatography for the analysis of phthalate esters in cosmetic and environmental water samples. Microchem J 99, 26-33 (2011). 9. Staples, C.A., Peterson, D.R., Parkerton, T.F. & Adams, W.J. The environmental fate of phthalate esters: A literature review. Chemosphere 35, 667-749 (1997). 10. Zhang, H., Chen, X.Q. & Jiang, X.Y. Determination of phthalate esters in water samples by ionic liquid cold-induced aggregation dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography. Anal Chim Acta 689, 137-142 (2011). 11. Ruuska, R.M., Korkeala, H., Liukkonenlilja, H., Suortti, T. & Salminen, K. Migration of Contaminants from Milk Tubes and Teat Liners. J Food Protect 50, 316-320 (1987). 12. Vessman, J. & Rietz, G. Determination of Di(Ethylhexyl) Phthalate in Human Plasma and Plasma-Proteins by Electron-Capture Gas-Chromatography. J Chromatogr 100, 153-163 (1974). 13. Hellwig, J., Freudenberger, H. & Jackh, R. Differential prenatal toxicity of branched phthalate esters in rats. Food Chem Toxicol 35, 501-512 (1997). 14. Giam, C.S., Chan, H.S. & Neff, G.S. Rapid and Inexpensive Method for Detection of Polychlorinated Biphenyls and Phthalates in Air. Anal Chem 47, 2319-2320 (1975). 15. Schouten, M.J., Peereboom, J.W.C. & Brinkman, U.A.T. Liquid-Chromatographic Analysis of Phthalate-Esters in Dutch River Water. Int J Environ an Ch 7, 13-23 (1979). 16. Schwartz, H.E., Anzion, C.J.M., Vanvliet, H.P.M., Peerebooms, J.W.C. & Brinkman, U.A.T. Analysis of Phthalate-Esters in Sediments from Dutch Rivers by Means of High-Performance Liquid-Chromatography. Int J Environ an Ch 6, 133-144 (1979). 17. Peterson, J.C. & Freeman, D.H. Method Validation of Gc-Ms-Sim Analysis of Phthalate-Esters in Sediment. Int J Environ an Ch 12, 277-291 (1982). 18. Russell, D.J., Mcduffie, B. & Fineberg, S. The Effect of Biodegradation on the Determination of Some Chemodynamic Properties of Phthalate-Esters. J Environ Sci Heal A 20, 927-941 (1985). 19. Pollack, G.M., Slaughter, R.L., Buchanan, J.F. & Shen, D.D. High-Performance Liquid-Chromatographic Procedure for the Determination of Di-(2-Ethylhexyl)Phthalate in Human-Blood Specimens - Problems of Variable-Extraction Yield and the Use of Standard Addition for Calibration. J Chromatogr 311, 101-108 (1984). 20. Albro, P.W., Jordan, S.T., Schroeder, J.L. & Corbett, J.T. Chromatographic-Separation and Quantitative-Determination of the Metabolites of Di-(2-Ethylhexyl) Phthalate from Urine of Laboratory-Animals. J Chromatogr 244, 65-79 (1982). 21. Vilaplana, F., Martinez-Sanz, M., Ribes-Greus, A. & Karlsson, S. Emission pattern of semi-volatile organic compounds from recycled styrenic polymers using headspace solid-phase microextraction gas chromatography-mass spectrometry. J Chromatogr A 1217, 359-367 (2010). 22. Batlle, R. & Nerin, C. Application of single-drop microextraction to the determination of dialkyl phthalate esters in food simulants. J Chromatogr A 1045, 29-35 (2004). 23. Arthur, C.L. & Pawliszyn, J. Solid-Phase Microextraction with Thermal-Desorption Using Fused-Silica Optical Fibers. Anal Chem 62, 2145-2148 (1990). 24. Psillakis, E. & Kalogerakis, N. Hollow-fibre liquid-phase microextraction of phthalate esters from water. J Chromatogr A 999, 145-153 (2003). 25. Kelly, M.T. & Larroque, M. Trace determination of diethylphthalate in aqueous media by solid-phase microextraction-liquid chromatography. J Chromatogr A 841, 177-185 (1999). 26. Penalver, A., Pocurull, E., Borrull, F. & Marce, R.M. Determination of phthalate esters in water samples by solid-phase microextraction and gas chromatography with mass spectrometric detection. J Chromatogr A 872, 191-201 (2000). 27. Luks-Betlej, K., Popp, P., Janoszka, B. & Paschke, H. Solid-phase microextraction of phthalates from water. J Chromatogr A 938, 93-101 (2001). 28. Moder, M., Popp, P. & Pawliszyn, J. Characterization of water-soluble components of slurries using solid-phase microextraction coupled to liquid chromatography mass spectrometry. J Microcolumn Sep 10, 225-234 (1998). 29. Feng, Y.L., Zhu, J.P. & Sensenstein, R. Development of a headspace solid-phase microextraction method combined with gas chromatography mass spectrometry for the determination of phthalate esters in cow milk. Anal Chim Acta 538, 41-48 (2005). 30. Hou, L. & Lee, H.K. Determination of pesticides in soil by liquid-phase microextraction and gas chromatography-mass spectrometry. J Chromatogr A 1038, 37-42 (2004). 31. Wang, Y., Kwok, Y.C., He, Y. & Lee, H.K. Application of dynamic liquid-phase microextraction to the analysis of chlorobenzenes in water by using a conventional microsyringe. Anal Chem 70, 4610-4614 (1998). 32. Zhao, R.S., Lao, W.J. & Xu, X.B. Headspace liquid-phase microextraction of trihalomethanes in drinking water and their gas chromatographic determination. Talanta 62, 751-756 (2004). 33. de Jager, L.S. & Andrews, A.R.J. Development of a screening method for cocaine and cocaine metabolites in urine using solvent microextraction in conjunction with gas chromatography. J Chromatogr A 911, 97-105 (2001). 34. Psillakis, E. & Kalogerakis, N. Application of solvent microextraction to the analysis of nitroaromatic explosives in water samples. J Chromatogr A 907, 211-219 (2001). 35. Carlsson, K. & Karlberg, B. Monosegmented micro-volume liquid-liquid flow-extraction system based on intermittent pumping and spectroscopic detection. Anal Chim Acta 415, 1-7 (2000). 36. Theis, A.L., Waldack, A.J., Hansen, S.M. & Jeannot, M.A. Headspace solvent microextraction. Anal Chem 73, 5651-5654 (2001). 37. Melwanki, M.B., Hsu, W.H. & Huang, S.D. Determination of clenbuterol in urine using headspace solid phase microextraction or liquid-liquid-liquid microextraction. Anal Chim Acta 552, 67-75 (2005). 38. Shen, G. & Lee, H.K. Hollow fiber-protected liquid-phase microextraction of triazine herbicides. Anal Chem 74, 648-654 (2002). 39. Farahani, H., Ganjali, M.R., Dinarvand, R. & Norouzi, P. Screening method for phthalate esters in water using liquid-phase microextraction based on the solidification of a floating organic microdrop combined with gas chromatography-mass spectrometry. Talanta 76, 718-723 (2008). 40. Zhang, Y.F. & Lee, H.K. Low-density solvent-based vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction combined with gas chromatography-mass spectrometry for the fast determination of phthalate esters in bottled water. J Chromatogr A 1274, 28-35 (2013). 41. Yan, H.Y., Cheng, X.L. & Liu, B.M. Simultaneous determination of six phthalate esters in bottled milks using ultrasound-assisted dispersive liquid-liquid microextraction coupled with gas chromatography. J Chromatogr B 879, 2507-2512 (2011). 42. Liang, P., Xu, J. & Li, Q. Application of dispersive liquid-liquid microextraction and high-performance liquid chromatography for the determination of three phthalate esters in water samples. Anal Chim Acta 609, 53-58 (2008). 43. Farahani, H., Norouzi, P., Dinarvand, R. & Ganjali, M.R. Development of dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry as a simple, rapid and highly sensitive method for the determination of phthalate esters in water samples. J Chromatogr A 1172, 105-112 (2007). 44. Skoog, D.A., Holler, F.J. & Nieman, T.A. Principles of instrumental analysis, Edn. 5th. (Saunders College Pub. ; Harcourt Brace College Publishers, Philadelphia Orlando, Fla.; 1998). 45. Hoffmann, E.D. & Stroobant, V. Mass spectrometry principle and applications. 16 (2007). 46. Hoffmann, E.D. & Stroobant, V. Mass spectrometry principle and applications. 90 (2007). 47. 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). 48. Dagnac, T., Garcia-Chao, M., Pulleiro, P., Garcia-Jares, C. & Llompart, M. Dispersive solid-phase extraction followed by liquid chromatography-tandem mass spectrometry for the multi-residue analysis of pesticides in raw bovine milk. J Chromatogr A 1216, 3702-3709 (2009). 49. Li, N. et al. A modified QuEChERS method for the determination of some herbicides in yogurt and milk by high performance liquid chromatography. Talanta 105, 219-228 (2013). 50. 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. J Sep Sci 33, 600-609 (2010). 51. Romero-Gonzalez, R., Frenich, A.G., Vidal, J.L.M., Prestes, O.D. & Grio, S.L. Simultaneous determination of pesticides, biopesticides and mycotoxins in organic products applying a quick, easy, cheap, effective, rugged and safe extraction procedure and ultra-high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1218, 1477-1485 (2011). 52. Lehotay, S.J., Mastovska, K. & Lightfield, A.R. Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables. J AOAC Int 88, 615-629 (2005).
摘要: 
摘要

  塑膠製品為目前現代生活中不可或缺的之用品,但做為塑膠原料的苯乙烯 (styrene)、苯乙酮 (acetophenone)以及為了增加塑膠柔軟度所添加的鄰苯二甲酸酯類塑化劑 (plasticizer),卻會因為所盛裝的物品與溫度之關係,釋放至食品中。此類化合物為內分泌干擾物 (endocrine disrupting chemicals, EDCs) 之一種,主要會干擾生物體內分泌系統之正常運作,進而改變生殖或發育現象,甚至造成部分物種的去雄性與雌性化,導致生殖力降低。因此開發一快速與靈敏的分析方法偵測食品中所含微量塑膠原料與塑化劑,對食品安全是一重要之課題。本研究主要開發 QuEChERS 萃取法結合氣相層析質譜術,偵測飲品中所含微量苯乙烯、苯乙酮、鄰苯二甲酸二甲酯 (dimethyl phthalate,DMP)、鄰苯二甲酸二乙酯 (diethyl phthalate,DEP) 與鄰苯二甲酸二丁酯 (di-n-butyl phthalate,DBP)。
  實驗結果於QuEChERS萃取乳酸飲料中分析物,取5 mL 市售乳酸飲料內含10 ng/mL 作為內標準品之4-甲基苯乙烯,再加入2 mL 乙酸乙酯之萃取溶劑與250 mg 無水硫酸鎂於玻璃離心管,震盪1分鐘後放入離心機,以4000 rpm 轉速離心5分鐘,取出上清液1 mL 至另一玻璃離心管,再加入45 mg之 一級二級胺 (primary secondary amine, PSA) 吸附劑和30 mg 無水硫酸鎂,震盪0.5分鐘後放入離心機,以4000 rpm 轉速離心3分鐘,所得上清液取1 μL 注入氣相層析質譜儀,使用電子游離法將分析物離子化後,再以選擇離子偵測 (selected ion monitoring,SIM)模式檢測。實驗結果顯示,五種分析物之線性範圍為0.05至100 ng/mL,線性相關係數皆在0.9928以上。五種分析物之偵測極限介於0.6 pg/mL (styrene)至 2.1 pg/mL (DMP),定量極限介於 2.1 pg/mL (styrene) 至7.1 pg/mL (DMP)。同日內與異日間之相對標準偏差分別為1.3至13.3% 與5.9至16.5%。
  應用本研究所開發方法對於市售乳酸飲料商品進行檢測,styrene 含量介於1.0至9.3 ng/mL;而 acetophenone 於市售樣品中並未檢測到;DMP 含量介於2.6至3.1 ng/mL;DEP 含量介於0.2至3.2 ng/mL;DBP 含量介於19.0至26.2 ng/mL,回收率介於94.2至105.9 %。結果顯示,所開發方法可作為未來檢測乳酸飲料中此類化合物之參考。

Abstract

  The plastic containers are widely used to pack various foods; however, the raw materials and plasticizers of plastic products may release into foods due to the long storage time or high storage temperature. These compounds are called endocrine disrupting chemicals (EDCs) and harmful to living organisms. Therefore, developing a rapid and sensitive method to analyze trace ingredient of plastic and plasticizers in beverage is very important in food safety issue. In this study, QuEChERS coupled with gas chromatography-mass spectrometry was developed to determine trace styrene, acetonphenone, and three useful phthalates in beverages. The optimal QuEChERS extraction conditions for extraction of trace styrene, acetophenone, dimethyl phthalate (DMP), diethyl phthalate (DEP), and di-n-butyl phthalate (DBP) in beverages were systematically evaluated in this study.
  In QuEChERS extraction, an aliquot of 5 mL of beverage samples included with 4-methylstyrene used as internal standard at the concentraction of 10 μg/mL was placed in a glass centrifuge tube and then 2.0 mL ethyl acetate used as extraction solvent and 250 mg anhydrous magnesium sulphate were added into the same tube. The glass centrifuge tube was shaken for 1 min by the vortex and subsequently centrifuged at 4000 rpm for 5 min. After centrifuging, the supernatant was transferred to another glass centrifuge tube containing 45 mg primary secondary amine (PSA) sorbent and 30 mg anhydrous magnesium sulphate. After vigorously shaking for 0.5 min, the tube was centrifuged at 4000 rpm for 3 min and the supernatant was transferred into a glass vial. An aliquot of 1 μL extractant was injected into GC-MS for analysis. The linearities of method proposed for the five analytes were from 0.05 to 100 ng/mL. The limits of detection (LODs) were from 0.6 (Styrene) to 2.1 (DMP) pg/mL. The relative standard deviation (RSD) of intra-day and inter-day precision were 1.3-13.3 % and 5.9-16.5 %, respectively. The recoveries of QuEChERS for extraction five analytes from beverages were from 94.2 to 105.9%. The method proposed was applied to analyze the commercial beverage. The results showed that concentration of styrene was from 1.0 to 9.3 ng/mL; the concentration of acetophenone was not detected; the concentration of DMP was from 2.6 to 3.1 ng/mL; the concentration of DEP was from 0.2 to 3.2 ng/mL; the concentration of DBP was from 19.0 to 26.2 ng/mL. Results of this study demonstrate the adequacy of QuEChERS-GC-MS method for determination of trace styrene, acetophenone, and three useful phthalates in beverages samples.
URI: http://hdl.handle.net/11455/14279
其他識別: U0005-1508201313431800
Appears in Collections:化學系所

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