Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16744
標題: 以微透析萃取結合次臨界水離子對層析法分析水樣中苯氧酸系除草劑
Determination of phenoxy acidic herbicides in environmental water sample by microdialysis extraction coupled subcritical water ion-pair chromatography
作者: 王嘉鵬
Wang, Chia-Peng
關鍵字: subcritical water ion-pair chromatography
苯氧酸系除草劑
microdialysis extraction
微透析萃取
次臨界水離子對層析法
出版社: 化學系所
引用: 1. 蔣慕錟、蔣永正,台灣旱田雜草之種類、生態及危害,1983,中華民國雜草學會彙刊,(4),30-41。 2. 蔡竹固,殺草劑之化學分類,1996,嘉義農專農藝學報,28:21-43。. 3. 蔣慕琰、蔣永正著,農田雜草管理及除草劑簡介,2001,行政院農業委員會農業藥物毒物試驗所編印,69頁。. 4. 王一雄,除草劑化性與環境中殘留,中華民國93 年6月,中華民國雜草學會會刊,第二十五卷第一期。. 5. Lynge, E., Cancer incidence in Danish phenoxy herbicide workers, 1947-1993. Environ Health Perspect, 1998, 106, 683-688. 6. Pozo, O.; Pitarch, E.; Sancho, J. V.; Hernandez, F., Determination of the herbicide 4-chloro-2-methylphenoxyacetic acid and its main metabolite, 4-chloro-2- methylphenol in water and soil by liquid chromatography- electrospray tandem mass spectrometry. Journal of Chromatography, A, 2001, 923, (1-2), 75-85. 7. Lagan, A.; Bacaloni, A.; De Leva, I.; Faberi, A.; Fago, G.; Marino, A., Occurrence and determination of herbicides and their major transformation products in environmental waters. Analytica Chimica Acta, 2002, 462, (2), 187-198. 8. Palma, G.; Sanchez, A.; Olave, Y.; Encina, F.; Palma, R.; Barra, R., Pesticide levels in surface waters in an agricultural-forestry basin in Southern Chile. Chemosphere, 2004, 57, (8), 763-770. 9. Takino, M.; Daishima, S.; Nakahara, T., Automated on-line in-tube solid-phase microextraction followed by liquid chromatography/electrospray ionization- mass spectrometry for the determination of chlorinated phenoxy acid herbicides in environmental waters. Analyst, 2001, 126, (5), 602-608. 10. Rodriguez, I.; Rub, E.; Gonzalez, R.; Quintana, J. B.; Cela, R., On-fibre silylation following solid-phase microextraction for the determination of acidic herbicides in water samples by gas chromatography. Analytica Chimica Acta, 2005, 537, (1-2), 259-266. 11. Rodriguez Pereiro, I.; Gonzalez Irimia, R.; Rubi Cano, E.; Cela Torrijos, R., Optimisation of a gas chromatographic-mass spectrometric method for the determination of phenoxy acid herbicides in water samples as silyl derivatives. Analytica Chimica Acta, 2004, 524, (1-2), 249-256. 12. Vink, M.; van der Poll, J. M., Gas chromatographic determination of acid herbicides in surface water samples with electron-capture detection and mass spectrometric confirmation. Journal of Chromatography, A, 1996, 733, (1-2), 361-366. 13. Zhu, L.; Lee, H. K., Field-amplified sample injection combined with water removal by electroosmotic flow pump in acidic buffer for analysis of phenoxy acid herbicides by capillary electrophoresis. Analytical Chemistry, 2001, 73, (13), 3065-3072. 14. Sekine, T.; H., Y., Solvent Extraction chemistry fundamental and Application. M. Dekker, 1977, 1932, 919. 15. Miller, J. M.; E., A. T., Liquid-liquid equilbrium and extraction. a literature source book, 1980. 16. Khan, S. U., Electron capture gas-liquid chromatographic method for the simultaneous analysis of 2,4-D, dicamba, and mecoprop residues in soil, wheat, and barley. Journal of the Association of Official Analytical Chemists, 1975, 58, (5), 1027-1031. 17.. Method 515.1,"Determination of Chlorinated Acid Herbicides in Water by Gas Chromatography with an Electron Capture Detector"Revision 4.0, U.S. Environmental Protection Agency, Office of Re-search and Development, Environmental Monitoring Systems Laboratory, Cincinnati, OH. 18. Arthur, C. L.; Pawliszyn, J., Solid phase microextraction with thermal desorption using fused silica optical fibers. Analytical Chemistry, 1990, 62, (19), 2145-2148. 19. Zhang, Z.; Yang, M. J.; Pawliszyn, J., Solid-Phase Microextraction. A Solvent- Free Alternative for Sample Preparation. Analytical Chemistry, 1994, 66, (17), 844A-854A. 20. Pawliszyn; J., Solid phase microextraction theory and practice. Wiley-VCH, 1997. 21. H.K. Koch, L. M. Gonzalez-Reche, J. Angerer, “On-line clean-up by multidimensional liquid chromatography-electrospray ionization tandem mass spectrometry for high throughput quantification of primary and second phthalate metabolites in human urine”, Journal of chromatography B, 2003, 784, 169. 22. J. K. Baker, “Characterization of phthalate plasticizers by HPLC/thermospray mass spectrometry”, Journal of Pharmaceutical and Biomedical Analysis, 1996, 15, 145. 23. Körner, K. H. Lund, U. Bolz, J. H. Petersen, “Identification and Quantification of Estrogenic Compounds in Recycled and Virgin Paper for Household G. Di Bella, M. Saitta, S. Lo Curto, F. Salvo, G. Licandro, G. Dugo, “Production Process Contamination of Citrus Essential Oils by Plastic Materials”, J. Agric. Food Chem. 2001, 49, 3705 24. A. M. Vinggaard, W. Use As Determined by an in Vitro Yeast Estrogen Screen and Chemical Analysis”, Chem. Res. Toxicol. 2000, 13, 1214 25. A. O. Earls, I. P. Axford, J. H. Braybrook, “Gas chromatography-mass spectrometry determination of migration of phthalate plasticisers from polyvinyl chloride toys and childcare articles”, Journal of Chromatography A, 2003, 983, 237. 26. J. D. Berset, R. Etter-Holzer, “Determination pf phthalates in crude extracts of sewage sludges by high-resolution capillary gas chromatography with mass spectrometry detection”, Journal of AOAC International, 2001, 84, 383. 27. 環署檢字第0910014627號公告NIEA R811.21C, “鄰苯二甲酸酯類檢測方法-氣相層析儀/電子捕捉偵測器法”, 2002. 28. L. Bito, H. Davson, E. Levin, M. Murray, N. Snider, J. Neurochem. 1966, 13, 1057. 29. J. M. Delgado, F. V. Defeudis, R.H. Roth, D. K. Ryugo, B. M. Mitruka, Arch. Int. Pharmacodyn. 1972, 198, 9. 30. U. Ungerstedt, “Microdialysis–A new bioanalytical sampling technique”, Current Separations, 1986, 7, 2. 31. R. D. Myers, “Methods for perfusing structure of the brain”, Met. Psych., 1972, 2, 169. 32. P. Redgrave, “In Vivo Perfusion and release of Neuroactive Substance”, Academic Press., London, 1985, 11. 33. I. D. Malonne, “A review of microdialysis sampling for pharmacokinetic applications”, Anal. Chim. Acta. , 1999, 379, 227. 34. S.J. Oh, S.-H. Moon, Thomas Davis,”Effects of metal ions on diffusion dialysis of inorganic acids”, J. Memb. Sci., 2000, 169, 95. 35. N. Torto, T. Laurell, L. Gorton, G. Marko-Varga, “Recent trends in the application of microdialysis in bioprocesses”, Anal. Chim. Acta., 1999, 379, 281. 36. H.G. Jayaratna, “Mercury Thread Electrode Modified with a Hydrophilic Dialysis Polymer” , Anal. Chem., 1994, 66, 2985. 37. S.D. Menacherry, J.B. Justice, Jr., “In Vivo Microdialysis and Thermospray Tandem Mass Spectrometry of the Dopamine Uptake Blocker 1-〔2-〔Bis(4-fluorophenyl)methoxy〕ethyl〕-4-(3-phenylpropyl)-piperazine”, Anal. Chem., 1990, 62, 597. 38. F. Laganà, G. Barbieri, E. Drioli, “Direct contact membrane distillation:modelling and concentration experiments”, J. Memb. Sci., 2000, 166, 1. 39. S. Morais, M.I. Alcaina-Miranda, F, Lazaro, M. Planta, A. Maquieira, R. Puchades., “Evaluation of the dialysing yield of membranes with different composition.Application to the analysis of chloride in fruit juices by flow injection”, Anal. Chim. Acta., 1997, 353 , 245. 40. T.H. Tsai, F.C. Cheng, L.C. Hung, C.F. Chen, “Determination of unbound ceftriaxone in rat blood by on-line microdialysis and microbore liquid chromatography”, Int. J. Pharm., 1999, 193, 21. 41. T. H. Tsai, F. C. Cheng, L. C. Hung, C. F. Chen, “On-line microdialysis coupled with microbore liquid chromatography for the determination of unbound chlouamphenicol and its glucuronide in rat blood”, J. Chromatogr. B, 1998, 720, 165. 42. T.H. Tsai, F.C. Cheng, L.C. Hung, C.F. Chen, “Simultaneous measurement of cefuroxime in rat blood and brain by microdialysis and microbore liquid chromatography Application to pharmacokinetics”, J. Chromatogr. B, 1999, 735, 25. 43. F.C. Cheng, D.Y. Yang, T.F. Wu, S.H. Chen, “Rapid on-line microdialysis hyphenated technique for the dynamic monitoring of extracellular pyruvate, lactic acid and ascorbic acid during cerebral ischemia”, J. Chromatogr. B, 1999, 723, 31. 44. M. W. Lada, T. W. Vickroy, R. T. Kennedy, “High Temporal Resolution Monitoring of Glutamate and Aspartate in Vivo Using Microdialysis On-Line with Capillary Electrophoresis with Laser-Induced Fluorescence Detection”, Anal. Chem., 1997, 69, 4560. 45. M.I. Davies, C.E. Lunte, “Microdialysis sampling coupled on-line to microseparation techniques” Soc. Rev. Chem., 1997, 26, 215. 46. Z. H. Lin, L.W. Burgess, “Chemically Facilitated Donnan Dialysis and Its Application in a Fiber Optic Heavy Metal Sensor”, Analytical Chemistry, 1994, 66, 2544. 47. J. F. van Staden, C. J. Hattingh, “Preconcentration of an analyte dialysate in a flow-injection system”, Analytica Chimica Acta, 1995, 308, 214. 48. V. Kislik, A. Eyal, “Aqueous hybrid liquid membrane process for metal separation Part I. A model for transport kinetics and its experimental verification”, Journal of Membrane Science, 2000, 169, 119. 49. T. Kobayashi, X. Chai, N. Fujii, “Ultrasound enhanced cross-flow membrane filtration”, Separation and Purification Technology, 1999, 17, 31. 50. S. A. Wages, W. H. Church, J. B. Justice, Jr., “Sampling Considerations for On-line Microbore Liquid Chromatography of Brain Dialysate”, Analytical Chemistry, 1986, 58, 1649. 51. M. Hichour, F. Persin, J. Molénat, J. Sandeaux, C. Gavach, “Fluoride removal from diluted solutions by Donnan dialysis with anion-exchange membranes”, Desalination, 1999, 122, 53. 52. Y. P. Zhao, X. H. Liang, C. E. Lunte, “Comparison of recovery and delivery in vitro for calibration of microdialysis probes”, Analytica Chimica Acta, 1995, 316, 403. 53. T.-D. Martin, D.O. Scott, C. E. Lunte, “Intravenous Microdialysis Sampling in Awake, Freely-Moving Rats”, Analytical Chemistry, 1992, 64, 806. 54. L. Groth, A. Jørgensen, “In vitro microdialysis of hydrophilic and lipophilic compounds”, Analytica Chimica Acta, 1997, 355, 75. 55. R. Gawronski, B. Wrzeainska, “Kinetics of solvent extraction in hollow-fiber contactors”, Journal of Membrane Science, 2000, 168, 213. 56. Walrafen G E , Chu Y C. Raman Spectra from Water Vapor to the Supercritical Fluid[J ] . J Phys Chem. B ,1999 ,103 :1332 (1338. 57. Antia, F. D.; Horvath, C. “High-performance liquid chromatography at elevated temperatures: examination of conditions for the rapid separation of large molecules” J. Chromatogr. 1988, 435, 1-15 58. Jung-Ah Han and Seung-Taik Lim, CARBOHYDRATE POLYMERS 2004, 55:3:265-272 59. Silva-Lucca, R.A., Tabak, M., Nascimento, O.R., Roque-Barreira, M.C., Beltramini, L.M. (1999) Structural and thermodynamics studies of KM+, a D-mannose binding lectin from Artocarpus integrifolia seeds. Biophys. Chem 79, 81-93 60. Cirilli R., Costi R., Santo R. Di, Artico M., Roux A., Gallinella B., Zanitti L., Torre F. La” Enantioselective liquid chromatography of C3-chiral 2,3-dihydro-1,2,5-benzothiadiazepin-4(5H)-one and thione 1,1-dioxides on polyacrylamide- and polysaccharide-based chiral stationary phases”, J. Chromatogr. A, 2003, 993:1-2:17-28 61. Lili Zhou, Richard Thompson, Robert A. Reamer, Carrie Miller, Chris Welch, Dean K. Ellison and Jean M. Wyvratt.” Mechanistic study of enantiomeric recognition with native -cyclodextrin by capillary electrophoresis, reversed-phase liquid chromatography, nuclear magnetic resonance spectroscopy, electrospray mass spectrometry and circular dichroism techniques”, J. Chromatogr. A, 2003,987:1-2:409-420 62. David J. Miller and and Steven B. Hawthorne” Subcritical Water Chromatography with Flame Ionization Detection”, Anal. Chem., 1997, 69(4): 623-627. 63. Blackwell John A, Stringham Rodger W, Weckwerth Jeff D” Effect of Mobile Phase Additives in Packed-Column Subcritical and Supercritical Fluid Chromatography”, Anal. Chem, 1997, 69(3): 409-415. 64. Roger M, Robea J” Superheated waer as an eluent for reversed-phase high-performance liquid chromatography”, J. Chromatogr. A, 1997, 785: 49. 65. Trna M P, Colin F P” Salvation characterristics of pressurized hot water and its use in chromatography”, Anal Common, 1999, 38: 71. 66. 呂秀陽,何龍,鄭贊勝,蔡磊,化工進展 2003, 5: 477-481 67. David J. Miller and and Steven B. Hawthorne” Method for Determining the Solubilities of Hydrophobic Organics in Subcritical Water”, Anal. Chem. , 1998, 70 ( 8): 1618—1621 68. Greibrokk Tyge, Andersen Thomas” High-temperature liquid chromatography”, J Chromatogr. A, 2003,1000:743-755 69. Yang Yu, Lamm Lori J, He Ping, Kondo Toru “Temperature effect on peak width and column efficiency in subcritical water chromatography.”, J. Chromatogr. Sci., 2002, 40(2): 107-112. 70. Yang Yu, Jones Aaryn D, Mathis John A, Francis Melissa A, “Flame ionization detection after split t ing the water effluent in subcritical water chromatography “J. Chromatogr. A, 2002, 942(1-2): 231-236. 71. He Ping, Yang Yu “Studies on the long-term thermal stability of stationary phases in subcritical water chromatography”, J. Chromatogr. A, 2003, 989(1):55-63. 72. Lamm. Lori J, Yang Yu “Off-line coupling of subcritical water extraction with subcritical water chromatography via a sorbent trap and thermal desorption”., Anal. Chem, 2003, 75(10): 2237-2242. 73. Li B, Yang Y, Gan Y, Eaton C D, He P, Jones A D” On-line coupling of subcritical water extraction with high-performance liquid chromatography via solid-phase trapping.”, J. Chromatogr. A, 2000, 873(2): 175-84. 74. Jones Aaryn, Yang Yu “Separation of nonpolar analytes using methanol-water mixtures at elevated temperatures.”, Anal. Chim. Acta, 2003, 485(1): 51-55. 75. Kondo Toru, Yang Yu” Comparison of elution strength, column efficiency, and peak symmetry in subcritical water chromatography and traditional reversed-phase liquid chromatography.”, Anal. Chim. Acta, 2003, 494(1-2): 157-166. 76. 吳仁銘, 化學進展, 2002, 14( 1):32-36 77. 韓海,于榮敏, 王歡, 孫平華, 兒科藥學雜誌, 2003, 9(4): 11-12 78. Renn, C. N.; Synovec, R. E.” Refractive index gradient detection of biopolymers separated by high-temperature liquid chromatography” J. Chromatogr., A 1991, 536, 289-301. 79. Lima, L. R.; Synovec, R. E.” Uncoupling the effects of convection and diffusion on refractive index gradient detection in high-temperature liquid chromatography” Anal. Chem. 1993, 65, 128-134. 80. G Liu ,L Svenson ,N Djordgevic and F Erni , “Extra-column band broadening in HT – OTLC”, ibid. ,1993 ,633 :251 81. David J, Steven B” Subcritical Water Chromatography with Flame Ionization Detection”, Anal Chem., 1997, 69: 623 82. 李玲, 陸峰, 孫鵬, 原永芳, 吳玉田, 藥學學報, 2000, 35(11): 832 - 834 83. Lu F, Li L, Sun P, Wu Y T, Journal of Chinese Pharmaceutical Science, 2001, 10(1): 39-41 84. Ingelse, B. A.; Janssen, H. G.; Cramers, C. A. “HPLC-FID with superheated water as the eluent. Improved methods and instrumentation “ J. High Resolut. Chromatogr. 1998, 21, 613-616. 85. Smith R M, Burgess R J” Superheated water - a clean eluent for reversed-phase high-performance liquid chromatography”, Anal. Commun., 1996, 33: 327-329 86. Zhao, J.; Carr, P. W.” A comparative study of the chromatographic selectivity of polystyrene-coated zirconia and related reversed-phase materials “ Anal. Chem. 2000, 72, 302 87. T. S. Kephart and P. K. Dasgupta” Hot Eluent Capillary Liquid Chromatography using Zirconia and Titania based Stationary Phases.”, Anal. Chim. Acta, 2000, 414:71 88. Bruckner, C. A.; Ecker, S. T.; Synovec, R. E.” Simultaneous Flame Ionization and Absorbance Detection of Volatile and Nonvolatile Compounds by Reversed Phase Liquid Chromatography with a Water Mobile Phase” Anal. Chem. 1997, 69, 3465. 89. Bratha, A.; Vigh, Gy. Studies in reversed-Phase Ion-Pair Chromatography: 1. Adsorption Isotherms of Tetraalkylammonium Ion-Pair Reagents of Lichrosorb RP-18 in Methanol-Water Eluent. J. chromatogr. , 1983, 260, 337-345. 90. Jan Stahlberg; Ingela Hagglund. Adsorption Isotherm of Tabutylammonium Ion and Its Relation to the Mechanism of Ion Pair Chromatography. Anal. Chem. , 1988, 60, 1958-164. 91. ISkandarani, Z. ; Pietrzyk, D. J. Determination of Nitrite and Nitrate in water and Food Samples by Ion Interaction Chromatography. Anal. Chem. , 1982, 54, 2601-2603. 92. Tetsuo Okada. Micelle exclusion Chromatography of Inorganic Anions. Anal. Chem. , 1988, 60, 1511-1516.
摘要: 苯氧酸系除草劑為有機氯農藥的一種,由於其羧酸之特性,易形成離子態,透過地表流逕或土壤淋洗作用而傳輸到地下水,進一步威脅飲用水安全。本研究開發對環境水樣品中的苯氧酸系除草劑綠色檢測法。 將純水加熱至超過沸點後施加足夠壓力使其保持在液態,即稱之為次臨界水。其極性及介電常數隨溫度上升而下降,而與有機溶劑有相似的性質,因此可用於取代傳統HPLC的有機沖提液。本研究使用水溶液為動相,以 Hamilton PRP-1管柱對苯氧酸系除草劑做分離,因分析物帶有強極性的酸根,只使用純水作為動相分離效果並不理想,因此本實驗在動相中添加離子對試劑CH3NH3+,吸附在靜相上的CH3NH3+與分析物之酸根結合後,可增加分析物在管柱中的滯留效果。此種以離子對方式於分離管柱中分離陰離子的方法稱為離子對層析法 ( Ion-pair Chromatography )。 研究中利用微透析萃取結合次臨界水離子對層析法分析水樣中苯氧酸系除草劑,檢測對象包括2,4-D、MCPP、2,4,5-T。取15cm之醋酸纖維透析膜,灌流萃取液使用正辛醇,對30 mL水樣品(調整至pH 2),在400 rpm磁石攪拌下靜態萃取30 min後,以1μL/min的流速進樣17分鐘,將萃取液直接連線推入進樣閥,再以次臨界水離子對層析系統分析。以本方法最佳條件分析2,4-D、MCPP及2,4,5-T,其線性範圍在10- 500 μg/L,其相關係數在0.9960-0.9992之間。偵測極限分別為2 μg/L(2,4-D)、4 μg/L(MCPP)、6 μg/L(2,4,5-T)。所發展之檢測技術,應用於農田溝渠水樣品,偵測到含有15 μg/L 的2,4-D、7 μg/L 的MCPP、9 μg/L的2,4,5-T殘留,回收率介於70-85%。
In this study, we have developed a novel green route analytical method for the determination of phenoxy acid herbicides (2,4-D, 2,4,5-T, and MCPP) in water sample using on-line microdialysis extraction coupled with subcritical water ion-pair chromatography. Microdialysis extraction liquid (1-Octanol) and Cellulose Acetate dialysis membrane were employed to extract the analytes from the agricultural water in Yunlin city, Taiwan. The Cellulose Acetate dialysis membrane was directly connected to the injection valve of subcritical water ion-pair chromatography system. After the microdialysis extraction, the extracted analytes were on-line introduced into the subcritical water separation column (Hamilton PRP-1) and detected by a UV detector. Under the optimal microdialysis extraction and subcritical water ion-pair chromatography conditions, the linear range for 2,4-D, MCPP and 2,4,5-T were 10-500 μg/L. The correlation coefficients were between 0.9960-0.9992. The limit of detection were 2 μg/L for 2,4-D, 4 μg/L for MCPP and 6 μg/L for 2,4,5-T. The recoveries of phenoxy acid herbicides in real sample (agricultural water) were between 70-85%. This method was using no organic solvent and could achieve good separation. The limits of detection were acceptable. So the proposed method provides a simple and eco-friendly procedure for isolating and determining phenoxy acid herbicides in agricultural water.
URI: http://hdl.handle.net/11455/16744
其他識別: U0005-2108200915453500
Appears in Collections:化學系所

文件中的檔案:

取得全文請前往華藝線上圖書館



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