近年來，微型化及綠色化學的趨勢逐漸成為分析前處理的主流方向，強調快速、簡便、低成本及低污染。本文採用符合上述原則的動態三液相微萃取（Dynamic-LLLME），作為環境水樣中氯苯氧乙酸（o-CPA；p-CPA；2,4-D；2,4,5-T）及氯酚（2-CP；2,4-DCP；2,4,6-TCP；PCP）的濃縮萃取，並配合離子對液相層析（IP-HPLC）與PDA偵測器進行分離與分析。
本研究的氯苯氧乙酸及氯酚被嚴格規範其水中容許濃度，以五氯酚（PCP）最為嚴謹。為達低偵測極限，除前濃縮外，以離子對層析法沖提及分離陰離子態分析物，使氯酚與苯氧乙酸以陰離子態通過PDA偵測器，陰離子的顯著助色團效應（auxochromic effect）造成原光譜特性波長紅位移且吸收度增大，利用這些特性吸收峰定量可降低偵測極限並減少干擾。本文對於各項可能影響萃取效率的變因進行詳細探討，並實際應用本方法於真實水樣（水庫水及自來水）。
於最佳實驗條件下，方法偵測極限（MDLs）在0.06~0.5μg/L；線性相關係數（r2）在線性濃度範圍內均大於0.9982；線性濃度因不同化合物而異，大致落在0.5~500μg/L內；RSD (%)在2.6~6.5之間。兩真實水樣的相對添加回收率分別為84.1~107.3%及88.5~104.9%，顯示本分析方法不受基質干擾的影響，可成功應用於環境水樣中。

[1] 辛竹英, “國內農藥使用情況” 89年中日環境荷爾蒙學術研討會 (2000) 77.
[2] W. Farmletter, 1979. Doane Agriculture, Service, Inc. Washington, DC.
[3] T. Cserhati, E. Forgacs, “Phenoxyacetic Acids: Separation And Quantitative Determination” J. Chromatogr. B 717 (1998) 157.
[4] L. Zhu, K.H. Ee, L. Zhao, H.K. Lee, “Analysis of phenoxy herbicides in bovine milk by means of liquid–liquid–liquid microextraction with a hollow-fiber membrane” J. Chromatogr. A 963 (2002) 335.
[5] A.D. Corcia, M. Marchetti, R. Samperi, “Extraction And Isolation Of Phenoxy Acid Herbicides In Environmental Waters Using Two Adsorbents In One Minicartidge” Anal. Chem. 61 (1989) 1363.
[6] I.S. Kim, F.I. Sasinos, R.D. Stephens, J. Wang, M. Brown, “Determination Of Chlorinated Phenoxy Acid And Ester Herbcides In Soil And Water By Liquid Chromatography Particle Beam Mass Spectrometry And Ultraviolet Absorption Spectrophotometry” Anal. Chem. 63 (1991) 819.
[7] 陳仲強, “以液相微萃取法搭配高效能液相層析儀偵測水中苯乙酸除草劑”
國立清華大學化學研究所碩士論文 (2005)
[8] C. Baird, Environmental chemistry, 2nd edn., W.H. Freeman, New York, 1999, p. 331.
[9] 2006 Edition of the Drinking Water Standards and Health Advisories, Office of Water, U.S. Environmental Protection Agency, Washington, DC.
[10] 行政院環境保護署環署毒字第0960100652號, 民國97年1月2日.
[11] 工業技術研究院工業技術發展中心, 危險物（一）環保署新公告十三種毒化物標示與物質安全資料範例, 1994.
[12] 金相燦, 程振華, 徐南妮, 李海生, 環境毒物有機污染物化學, 1st edn., 淑馨出版社, 1998.
[13] 江文仁, 袁紹英, 張碧芬, 潘子明, 環境研究中心環境調查年報, 1993.
[14] http://water.kinmen.gov.tw/html/service/qanda5.html#q1
[15] 環署檢字第26440號公告NIEA R106.00C, 民國八十五年六月.
[16] 環署檢字第31086號公告NIEA R107.00C, 民國八十五年六月.
[17] 環署檢字第72570號公告NIEA R113.00C, 民國八十五年十二月.
[18] 環署檢字第64195號公告NIEA R114.00C, 民國八十五年十一月.
[19] D.E. Raynie, “Modern Extraction Techniques” Anal. Chem. 76 (2004) 4659.
[20] D.E. Raynie, “Modern Extraction Techniques” Anal. Chem. 78 (2006) 3997.
[21] M. Saraji, “Dynamic Headspace Liquid-Phase Microextraction Of Alcohols” J. chromatogr. A 1062 (2005) 15.
[22] D.A. Skoog, F.J. Holler, T.A. Nieman, Principles of Instrumental Analysis, 5th edn., Saunders College Publishing, USA, 1998, p. 768.
[23] S. Scheppers, A. Wercinski, Solid Phase Microextraction-A Practical Guide, Varian Chromatography System Walnut Creet, California, 1999.
[24] C.L. Arthur, J. Pawliszyn, “Solid Phase Microextraction With Thermal Desorption Using Fused Silica Optical Fibers” Anal. Chem. 62 (1990) 2145.
[25] Y. Kotiaho, F.R. Jauristen, T.K. Choudhury, R.G. Cooks, G.T. Tsao, “Membrane Introduction Mass-Spectrometry” Anal. Chem. 63 (1991) 875.
[26] E. Psillakis, N. Kalogerakis, “Developments In Liquid-Phase Microextraction” Trends Anal. Chem. 22 (2003) 565.
[27] 環署檢字第31083號公告NIEA R104.00C, 民國八十五年六月.
[28] H. Liu, P.K. Dasgupta, “Analytical Chemistry in a Drop. Solvent Extraction in a Microdrop” Anal. Chem. 68 (1996) 1817.
[29] M.A. Jeannot, F.F. Cantwell, “Solvent Microextraction into a Single Drop” Anal. Chem. 68 (1996) 2236.
[30] M.A. Jeannot, F.F. Cantwell, “Mass Transfer Characteristics of Solvent Extraction into a Single Drop at the Tip of a Syringe Needle” Anal. Chem. 69 (1997) 235.
[31] Y. He, H.K. Lee, “Liquid-Phase Microextraction in a Single Drop of Organic Solvent by Using a Conventional Microsyringe” Anal. Chem. 69 (1997) 4634.
[32] M. Ma, F.F. Cantwell, “Solvent Microextraction with Simultaneous Back-Extraction for Sample Cleanup and Preconcentration: Preconcentration into a Single Microdrop” Anal. Chem. 71 (1999) 388.
[33] S. Pedersen-Bjergaard, K.E. Rasmussen, “Liquid-Liquid-Liquid Microextraction for Sample Preparation of Biological Fluids Prior to Capillary Electrophoresis” Anal. Chem. 71 (1999) 2650.
[34] G. Shen, H.K. Lee, “Hollow Fiber-Protected Liquid-Phase Microextraction of Triazine Herbicides” Anal. Chem. 74 (2002) 648.
[35] S. Pedersen-Bjergaard, K.E. Rasmussen, “Developments in hollow fibre-based, liquid-phase microextraction” Trends Anal. Chem. 23 (2004) 1.
[36] D. Kristof, D. Jo, D.W. Bavo, V.L. Herman, “Sample preparation for the analysis of volatile organic compounds in air and water matrices” J. Chromatogr. A 1153 (2007) 130.
[37] M. Rezaee, Y. Assadi, M.-R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, “Determination of organic compounds in water using dispersive liquid–liquid microextraction” J. Chromatogr. A 1116 (2006) 1.
[38] D. Nagaraju, S.D. Huang, “Determination of triazine herbicides in aqueous samples by dispersive liquid-liquid microextraction with gas chromatography-ion trap mass spectrometry“ J. Chromatogr. A 1161 (2007) 89.
[39] 鍾莉雯, 李茂榮, “液相微萃取法於水中微量氯酚的偵測” 國立中興大學化學研究所碩士論文 (2002)
[40] 劉文琳, 李茂榮, “開發超臨界流體與固相微萃取線上連結技術連結氣相層析質譜儀分析環境土壤中氯酚含量之研究” 第十三屆分析技術交流研討會 (2007) 96.
[41] C.Y. Lin, S.D. Huang, “Application of liquid–liquid–liquid microextraction and ion-pair liquid chromatography coupled with photodiode array detection for the determination of chlorophenols in water” J. Chromatogr. A 1193 (2008) 79.
[42] M.B. Melwanki, S.D. Huang, “Three-phase system in solvent bar microextraction:An approach for the sample preparation of ionizable organic compounds prior to liquid chromatography” Anal. Chim. Acta 555 (2006) 139.
[43] O. Pozo, E. Pitarch, J.V. Sancho, F. Herna´ndez, “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” J. Chromatogr. A 923 (2001) 75.
[44] L. Zhu, C. Tu, H.K. Lee, “Liquid-Phase Microextraction of Phenolic Compounds Combined with On-Line Preconcentration by Field-Amplified Sample Injection at Low pH in Micellar Electrokinetic Chromatography” Anal. Chem. 73 (2001) 5655.
[45] C. Basheer, H.K. Lee, “Analysis of endocrine disrupting alkylphenols, chlorophenols and bisphenol-A using hollow fiber-protected liquid-phase microextraction coupled with injection port-derivatization gas chromatography–mass spectrometry” J. Chromatogr. A 1057 (2004) 163.
[46] A. Kabir, C. Hamlet, A. Malik, “Parts per quadrillion level ultra-trace determination of polar and nonpolar compounds via solvent-free capillary microextraction on surface-bonded sol–gel polytetrahydrofuran coating and gas chromatography–flame ionization detection” J. Chromatogr. A 1047 (2004) 1.
[47] X. Jiang, S.Y. Oh, H.K. Lee, “Dynamic Liquid-Liquid-Liquid Microextraction with Automated Movement of the Acceptor Phase” Anal. Chem. 77 (2005) 1689.
[48] J. Zhang, T. Su, H.K. Lee, “Headspace Water-Based Liquid-Phase Microextraction” Anal. Chem. 77 (2005) 1988.
[49] Jingming Wu, K.H. Ee, H.K. Lee, “Automated dynamic liquid–liquid–liquid microextraction followed by high-performance liquid chromatography-ultraviolet detection for the determination of phenoxy acid herbicides in environmental waters” J. Chromatogr. A 1082 (2005) 121.
[50] M. Saraji, M. Bakhshi, “Determination of phenols in water samples by single-drop microextraction followed by in-syringe derivatization and gas chromatography–mass spectrometric detection” J. Chromatogr. A 1098 (2005) 30.
[51] J.f. Liu, Y.G. Chi, G.B. Jiang, “Screening the extractability of some typical environmental pollutants by ionic liquids in liquid-phase microextraction” J. Sep. Sci. 28 (2005) 87.
[52] Cunling Ye, Qingxiang Zhou, Xinming Wang, Junping Xiao, “Determination of phenols in environmental water samples by ionic liquid-based headspace liquidphase microextraction coupled with highperformance liquid chromatography” J. Sep. Sci. 30 (2007) 42.
[53] J.F. Peng, J.F. Liu, X.L. Hu, G.B. Jiang, “Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography” J. Chromatogr. A 1139 (2007) 165.
[54] J. Zhang, T. Su, H.K. Lee, “Development and application of microporous hollow fiber protected liquid-phase microextraction via gaseous diffusion to the determination of phenols in water” J. Chromatogr. A 1121 (2006) 10.
[55] Jingming Wu, H.K. Lee, “Injection Port Derivatization Following Ion-Pair Hollow Fiber-Protected Liquid-Phase Microextraction for Determining Acidic Herbicides by Gas Chromatography/Mass Spectrometry” Anal. Chem. 78 (2006) 7292.
[56] S. Moret, M. Hidalgo, J.M. Sa´nchez’, “Development of an Ion-Pairing Liquid Chromatography Method for the Determination of Phenoxyacetic Herbicides and Their Main Metabolites:Application to the Analysis of Soil Samples” Chromatographia 63 (2006) 109.
[57] N. Fattahi, Y. Assadi, M.R.M. Hosseini, E.Z. Jahromi, “Determination of chlorophenols in water samples using simultaneous dispersive liquid–liquid microextraction and derivatization followed by gas chromatography-electron-capture detection” J. Chromatogr. A 1157 (2007) 23.
[58] N. Fattahi, S. Samadi, Y. Assadi, M.R.M. Hosseini, “Solid-phase extraction combined with dispersive liquid–liquid microextraction-ultra preconcentration of chlorophenols in aqueous samples” J. Chromatogr. A 1169 (2007) 63.
[59] H. Xu, Y. Liao, Jinrong Yao, “Development of a novel ultrasound-assisted headspace liquid-phase microextraction and its application to the analysis of chlorophenols in real aqueous samples” J. Chromatogr. A 1167 (2007) 1.
[60] O. Chienthavorn, S. Pengpumkiat, A. Noomhormb, R.M. Smith, “Superheated water extraction and phase transfer methylation of phenoxy acid herbicides from solid matrices” J. Chromatogr. A 1152 (2007) 268.
[61] M. Saraji, B. Farajmand, “Application of single-drop microextraction combined with in-microvial derivatization for determination of acidic herbicides in water samples by gas chromatography–mass spectrometry” J. Chromatogr. A 1178 (2008) 17.
[62] 吳健三, 高效液相層析儀實務篇, 5th edn., 建宏層析企業股份有限公司, 2003, p. 40.
[63] D.A. Skoog, F.J. Holler, T.A. Nieman, Principles of Instrumental Analysis, 5th edn., Saunders College Publishing, USA, 1998, p. 334.
[64] M. Palit, D. Pardasani, A.K. Gupta, D.K. Dubey, “Application of Single Drop Microextraction for Analysis of Chemical Warfare Agents and Related Compounds in Water by Gas Chromatography/Mass Spectrometry” Anal. Chem. 77 (2005) 711.