本論文主要是利用固相微萃取法配合高效能液相層析儀 (SPME-HPLC)偵測自然界水中的五種雙苯醚類除草劑(diphenyl-ether herbicides)。這五種分別是Aclonifen、Bifenox、Fluoroglycofen-ethyl、Oxyfluorfen與Lactofen。
固相微萃取法是由Pawliszyn在1989年所提出的一種新萃取技術，由於它融合了採樣、萃取、濃縮與樣品導入的步驟，所以使這項技術用於前處理時能夠更加快速、便利。同時也因為萃取過程中不需要用到溶劑，故較為環保。此論文就是開發以這項技術，配合高效能液相層析儀分析上述五種化合物的方法。論文中將對於各項影響萃取效率的變因進行探討。這些變因包括用以萃取的纖維種類、萃取時間、脫附模式、浸泡時間、脫附時間、脫附液組成、萃取溫度、攪拌速率、夾帶殘留與樣品的pH值、有機溶劑強度、鹽類離子強度等十二項變因，同時檢測其線性相關係數、相對標準偏差和偵測極限。
本論文選擇利用PDMS/DVB和CW/TPR這兩支纖維偵測自然環境中的水溶液樣品。這兩支纖維所得到的回收率都在80%以上(PDMS/DVB的回收率為81~104 %，而CW/TPR為83~100 %)，這表示該水樣的基質干擾不算太嚴重。至於偵測極限方面，PDMS/DVB為0.33~1.74 ng/mL，CW/TPR為0.22~1.94 ng/mL。由此開發出利用SPME配合HPLC偵測水中雙苯醚類化合物的方法。

In this research, we develop a method of using solid-phase microextraction (SPME) coupled to high performance liquid chromatography (HPLC) to detect five diphenyl-ether type herbicides. They are aclonifen, bifenox, fluoroglycofen-ethyl, oxyfluorfen and lactofen.
Solid-phase microextraction is a new technique developed by Pawliszyn in 1989. The unique feature of this technique is that it combines sampling, extraction, concentration and sample injection in one step. It’s faster and simpler than other traditional pretreatment technique. It is also more friendly to our environment because it uses no organic solvents. In this thesis, we develop a method of using this with HPLC to detect the above five compounds. We investigate some variations that affect the efficiency of extraction including extraction fiber, extraction time, soaking time, desorption mode, component of desorption liquid, extraction temperature, stirring rate, carryover, sample pH value, organic solvent and salt addition. We also check it’s linearity correlation coefficient, relative standard deviation and detection limit.
We choose PDMS/DVB and CW/TPR these two fibers to detect water samples in our environment. The recovery of these two fibers are all above 80 % ( 81~104 % for PDMS/DVB and 83~100 % for CW/TPR fiber ), this shows that the interference from this water sample matrix is not too severe. The detection limit for PDMS/DVB is 0.33 ~ 1.74 ng/mL and CW/TPR 0.22 ~ 1.94 ng/mL. Finally, this thesis offers a way of detecting diphenyl-ethercompounds in water samples by SPME/HPLC.

一、序論
1-1 前言 ……………………………………………………………1
1-2 有機污染物的前處理方法 ……………………………………3
1-3 固相微萃取法 …………………………………………………7
二、實驗部分
2-1 藥品 ……………………………………………………………10
2-2 標準溶液與真實樣品 …………………………………………11
2-3 儀器裝置 ………………………………………………………11
2-4 實驗步驟 ………………………………………………………12
三、結果與討論
3-1 各項變因之探討
3-1-1 纖維的種類 ………………………………………………14
3-1-2 萃取時間 …………………………………………………15
3-1-3 脫附模式 …………………………………………………17
3-1-4 浸泡時間 …………………………………………………18
3-1-5 脫附液組成 ………………………………………………19
3-1-6 脫附時間 …………………………………………………20
3-1-7 夾帶殘留 …………………………………………………21
3-1-8 攪拌速率 …………………………………………………22
3-1-9 萃取溫度 …………………………………………………24
3-1-10 樣品溶液的pH值 …………………………………………26
3-1-11 有機溶劑的影響 …………………………………………27
3-1-12 鹽類的影響 ………………………………………………29
3-2 方法偵測極限、相對標準偏差和線性相關係數 ……………32
3-3 真實樣品的測試 ……………………………………………34
3-4 雙苯醚類化合物相關文獻之比較………………………………35
四、結論 ……………………………………………………………38
五、參考文獻 ……………………………………………………39

[1] Mabuchi, T.;Miura, Y.;Ohtsuka, T. J. Pest. Sci. 2002, 27,
pp.39-46
[2] Mustafee, T. P. Trop. Pest. Mang. 1991, 37, pp.245-251
[3] Altland, J. E.;Gilliam, C. H.;Wehtje, G. Horttechnology
2003, 13, pp.9-14
[4] Warabi, E.;Usui, K.;Tanaka, Y.;Matsumoto, H. Pest. Mang.
Sci. 2001, 57, pp.743-748
[5] Shoup, D. E.;Al-Khatib, K.;Peterson, D. E. Weed Sci. 2003,
51, pp.145-150
[6] ChemService “ Certificate of analysis ” CAS#42576-02-3,
CAS#42874-03-3, CAS#77501-63-4
[7] Tanabe, A.;Mitobe, H.;Kawata, K.;Sakai, M. J. Chromato. A
1996, 754, pp.159-168
[8] Scrano, L.;Bufo, S. A.;D’Auria M.;Emmelin, C. J. Photochem.
Photobio A : Chemistry 1999, 129, pp.65-70
[9] Ying, G. G.;Williams, B. Agri. Ecosys. Environ. 2000, 78,
pp.283-289
[10] Vischetti, C.;Marucchini, C.;Leita, L.;Cantone, P.;Danuso,
F.;Giovanardi, R. European Journal of Agronomy 2002, 16,
pp.231-238
[11] Lagana, A.;Bacaloni, A.;Leva, I. D.;Faberi, A.;Fago,
G.;Marino, A. Analytical Chimica Acta 2002, 462, pp.187-198
[12] Gao, J. P.;Maguhn, J.;Spitzauer, P.;Kettrup, A. Water
Research 1998, 32, pp.2089-2094
[13] Gao, J. P.;Maguhn, J. ;Spitzauer, P.;Kettrup, A. Water
Research 1997, 31, pp.2811-2819
[14] Matsumoto, H.;Kashimoto, Y.;Warabi, E. Pest. Biochem. and
Physio. 1999, 64, pp.47-53
[15] Yen, J. H.;Sheu, W. S.;Wang, Y. S. Ecotoxicology and
Environmental Safety 2003, 54, pp.151-156
[16] Oguri, A.;Karakama, K.;Arakawa, N.;Sugimura,
T.;Wakabayash, K. Mutation Research 1995, 346, pp.57-60
[17] Shirley, A. B.;Rachel, C. C. “ Basic guide to
pesticides : Their Characterristics and hazards ”
Hemisphere publishing Corporation, 1992
[18] Jinno, H.;Hatakeyama, N.;Hanioka, N.;Yoda, R. Food and
Chem. Toxico. 1999, 37, pp.69-74
[19] Geoffroy, L.;Teisseire, H.;Couderchet, M.;Vernet, G. Pest.
Biochem. Physio. 2002, 72, pp.178-185
[20] Skoog, D. A.;Holler, F. J. “ Principle of Instrumental
Analysis, 5th edition ” Suanders College Publish, USA
[21] Scheppers, S.;Wercinski, A. “ Solid-phase microextraction-
A Practical Guide ” Varian Chromatography System Walnut
Creet, California 1999, p.21
[22] Scheppers, S.;Wercinski, A. “ Solid-phase microextraction-
A Practical Guide ” Varian Chromatography System Walnut
Creet, California 1999, p.19
[23] Scheppers, S.;Wercinski, A. “ Solid-phase microextraction- A Practical Guide ” Varian Chromatography System Walnut
Creet,California 1999, p.20
[24] Zhang, Z.;Yang, M. J.; Pawliszyn, J. Anal. Chem. 1994, 66,
pp.844A-853A
[25] Arthur, C. L.;Killam, L. M.;Buchholz, K. D.;Pawliszyn,
J.;Berg, J. R. Anal. Chem. 1992, 64, pp.1960-1966
[26] Zhang, Z.;Pawliszyn, J. Anal. Chem. 1993, 65, pp.1843-1852
[27] Karen, D.;Buchholz;Pawliszyn, J. Anal. Chem. 1994, 66,
pp.160-167
[28] Eisert, R.;Pawliszyn, J. Anal. Chem. 1997, 69, pp.3140-3147
[29] Kataoka, H.;Narimatsu, S.;Lord, H. L.;Pawliszyn, J. Anal.
Chem. 1999, 71, pp.4237-4244
[30] Chen, J.;Pawliszyn, J. B. Anal. Chem. 1995, 67, pp.2530-
2533
[31] Boyd-Boland, A. A.;Pawliszyn, J. B. Anal. Chem. 1996, 68,
pp.1521-1529
[32] Aranda, R.; Burk, R.C. J. Chroma. A. 1998, 829, pp.401-406
[33] Wu, Y. C.;Huang, S. D. Anal. Chem. 1999, 71, pp.310-318
[34] Kelly, M. T.;Larroque, M. J. chromato. A. 1999, 841,
pp.177-185
[35] Wu, Y. C.;Huang, S. D. J. chromato. A. 1999, 835, pp.127
-135
[36] Tomlin, C. D. S. “ The pesticides manual, 12th edition ”
2000, The British Corp.
[37] Lagana, A.;Fago, G.;Fasciani, L.;Marino, A.;Mosso, M.
Anal. Chim. Acta 2000, 414, pp.79-94
[38] Anna, A.;Boland, B.;Magdic, S.;Pawliszyn, J. B. Analyst
1996, 121, pp.929-938
[39] Bao, M. L.;Pantani, F.;Barbieri, K.;Burrini, D.;Griffi, O.
Intern. J. Environ. Anal. Chem. 1996, 64, pp.233-245
[40] Tanabe, A.;Mitobe, H.;Kawata, K.;Sakai, M. J. Chromato. A
1996, 754, pp.159-168
[41] Ferrer, I.;Barcelo, D. J. chromato. A. 1999, 854, pp.197-
206
[42] Hogendoorn, E.; Van, Z. P. J. chromato. A. 2000, 892,
pp.435-453
[43] Xia, X. R.;Leidy, R. B. Anal. Chem. 2001, 73, pp.2041-2047
[44] Wu, J.;Pawliszyn, J. J. chromato. A. 2001, 909, pp.37-52