以液相微萃取法搭配氣相層析質譜儀偵測水樣中之有機化合物

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研究生：	陳珮珊
論文名稱：	以液相微萃取法搭配氣相層析質譜儀偵測水樣中之有機化合物
指導教授：	黃賢達
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	81
中文關鍵詞：	液相微萃取、殺蟲劑、水樣、有機磷農藥、質譜、衍生
外文關鍵詞：	liquid phase microextraction, pesticide, organophosphorus, hydroxycarbony, derivatization, gas chromatography
相關次數：	點閱：2 下載：0
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近年來，用來偵測水樣中微量污染物的樣品前處理方法不斷的創新發展，而液相微萃取法（liquid phase microextraction, LPME）即為備受矚目的萃取法之一。本篇論文以其為前萃取的步驟搭配氣相層析質譜儀(gas chromatography-mass spectrometry, GC-MS)來分析水樣中hydroxycarbonyl (3-hydroxy-2-butanone, hydroxyacetone，3-hydroxy-3-methyl-2-butanone，4-hydroxy-4-methyl-2-pentanone)以及四種有機磷農藥普伏松 (ethoprop)，大利松 (diazinon)，二硫松(disulfoton)，芬殺松 (fenthion)。
偵測hydroxycarbonyl所得到的偵測極限為0.022-4.78ng/l，檢量線皆涵蓋二個級數，其R2 都在0.994以上；精密度維持在4-10%內。在最佳化條件下，將hydroxycarbonyl添加在雨水與去離子水中比較，得到的相對回收率範圍皆大於86%。而針對真實樣品(1)與(2)，測得樣品(1) 含3-hydroxy-2-butanone 0.11μg/l與 hydroxyacetone 2.54 μg/l，而樣品(2)中含有 hydroxyacetone 2.39 μg/l。
分析有機磷農藥，所得到的偵測極限：0.20-0.01μg/l，檢量線皆涵蓋三個級數，其R2 都在0.996以上。在不同天的操作中其精密度維持在5-8%內。在最佳化條件下，將有機磷農藥分別添加在湖水中並與去離子水的水樣比較，所得到的相對回收率範圍皆大於83%。最後，比較本實驗與固相微萃取法的結果，得到液相微萃取法的偵測極限較低，更有潛力來偵測水樣中的有機磷農藥。

The trace-amount analysis has developed by a novel pre-treatment method, liquid phase microextraction (LPME), coupled to gas chromatography-mass spectrometry (GC-MS). The technique involves a fast, solvent-free, pre-concentration and small scale extraction to analyze the target compounds in aqueous samples.
The hydroxycarbonyl compounds were determined by using two steps
derivatizations. Dynamic- LPME was applied to the first derivatization,
and head-space single drop microextraction was utilized in the second
derivatization. The LOD varied from 0.022- 4.78μg/l. The calibration
curves were linear at lest 2 orders of magnitude with the R2 ≧0.9941.
The precision was within 4 - 11%.The relative recoveries in the rain
water were more than 86%. In real sample (1), it contained 2.54 μg/l of
hydroxyacetone and 0.11μg/l of 3-hydroxy-2-butanone. The
hydroxyacetone was also determined in the sample 2 at the concentration
of 2.39 μg/l.
Using 3.5μl organic solvent extracts organophosphorus pesticides in a 20ml aqueous sample. Under optimized conditions, the limits of detection (LOD) with unit Resolution Selected Ion Storage (uSIS) mode depended on the compounds and varied from 0.125 to 0.0055ng/l. The calibration curves were linear at least 3 orders of magnitude with the R2 ≧0.996. In general, the method also gave precision for inter-day and intra-day within 4 to 10%, and the relative recoveries in the lake water were ＞83% . Finally, the results were compared with solid phase microextraction (SPME). It showed that the LPME was an accurate and sensitive technique to detect trace pesticides in aqueous samples.

第一章緒論...........................................    1
1-1前言..............................................    1
1-2液相微萃取法(liquid phase microextraction,LPME)….    1
1-2-1單滴微萃取(single drop microextraction）.........    2
1-2-2動力-液相微萃取法(dynamic-LPME)..................    3
1-2-2-1二相動力-液相微萃取法(dynamic-LPME)...    ........    3
1-2-2-2三相動力-液相微萃取法(dynamic-LPME)    .........    4
1-2-3溶劑棒微萃取(solvent bar microextraction, SBME) …6
1-2-4薄膜輔助溶劑萃取(membrance-assisted solvent extraction)    ............8
1-3本論文研究方向    ....................................    8
1-4參考文獻    .....................................9
第二章    利用動力液相與單滴微萃取法同時衍生萃取雨水中多官能基化物.................................................15
2-1....................................................15
2-2實驗部份............................................18
2-2-1試劑..............................................18
2-2-2儲存標準溶液與工作標準溶..........................19
2-2-2-1儲存標準溶液液..................................19
2-2-2-2工作標準溶液....................................19
2-2-3儀器裝置裝........................................20
2-2-4定性    ..............................................21
2-2-5步驟    ..............................................21
2-2-5-1傳統衍生法......................................21
2-2-5-2液相微萃取法....................................21
2-3結果與討論..........................................22
2-3-1萃取溶劑的選擇....................................22
2-3-2萃取時間的探討....................................23
2-3-2-1第一段衍生萃取..................................23
2-3-2-2第二段衍生萃取..................................23
2-3-3攪拌速率的影響....................................24
2-3-3-1第一段衍生萃取..................................24
2-3-3-2第二段衍生萃取..................................24
2-3-4溫度的影響........................................24
2-3-5鹽類(NaCl)的影響..................................25
2-3-6環境樣品分析......................................26
2-3-7偵測極限..........................................26
2-3-8精密度與檢量線....................................27
2-3-9回收率與再現性....................................27
2-3-10液相微萃取與傳統合成法比較.......................27
2-4結論................................................28
2-5參考文獻............................................29
第三章以動力液相微萃取法搭配氣相層析質譜儀偵測水樣之有機磷農藥.....................................................54
3-1前言................................................54
3-2實驗部分............................................56
3-2-1試劑..............................................56
3-2-2儲存標準溶液與工作標準溶液........................56
3-2-2-1儲存標準溶液....................................56
3-2-2-2工作標準溶液....................................56
3-2-3儀器裝置..........................................57
3-2-4定性..............................................58
3-2-5步驟    ..............................................58
3-3結果與討論..........................................58
3-3-1萃取溶劑的選擇....................................58
3-3-2萃取時間的探討....................................59
3-3-3攪拌速率的影響....................................60
3-3-4鹽類(NaCl)的影響..................................60
3-3-5腐植酸(humic acid)的影響..........................61
3-3-6甲醇(methanol)的影響..............................61
3-3-7環境樣品的分析....................................61
3-3-8偵測極限與線性....................................61
3-3-9回收率與再現性....................................62
3-3-10液相微萃取與固相微萃取法比較.....................62
3-4結論................................................63
3-5參考文獻............................................64

                                

1-4 參考文獻
[1] Jeannot, M. A.; Cantwell, F. F. Anal. Chem. 1997, 69, 235-239.
[2] Zhao, L.; Lee, H. K. J. Chromatogr. A 2001, 919, 381–388
[3] Shen, G.; Lee, H.K. Anal. Chem. 2002, 74, 648-654.
[4] Hou, L.; Lee, K. H. Anal. Chem. 2003, 75, 2784-2789
[5] Jiang, X. M.; Lee, K. H. Anal. Chem. 2005, 77, 1689-1695
[6] Jiang, X. M.; Lee, H. K. Anal. Chem. 2004, 76, 5591-5596
[7] Schellin, M.; Hauser, B. J. Chromatogr. A 2004, 1041, 251–258.
[8] Basheer, C.; Lee, H. K. J. Chromatogr. A 2004, 1022, 161–169

2-5參考文獻
[1] Watson, J. G. J. Air Waste Manage. Assoc. 2002, 52, 628-713.
[2] Charlson, R. J.; Schwartz, S. E.; Hales, J. M.; Cess, R. D.; Coakley, J. A.; Hansen, J. E., Hoffmann, D. J. Science 1992, 255, 423-430.
[3] Haywood, J.; Boucher, O. Rev. Geophys. 2000, 38, 513-543.
[4] Ramanathan, V.; Crutzen, P. J.; Kiehl, J. T.; Rosenfeld, D. Science 2001, 294, 2119-2124.
[5] Samet, J. M.; Dominici, F.; Curriero, F. C.; Coursac, I.; Zeger, S. L. N. Eng. J. Med. 2000, 343, 1742-1749.
[6] Gamble, J. F. Environ. Health Perspect. 1998, 106, 535-549.
[7] Kubatova, A.; Vermeylen, R.; Claeys, M.; Cafmeyer, J. Atmos. Environ. 2000, 34, 5037-5051.
[8] Edney, E. O.; Kleindienst, T. E.; Conver, T. S.; McIver, C. D.; Weathers, W. S. Atmos. Environ. 2003, 37 (28), 3947-3965.
[9] Kesselmeier, J.; Staudt, M. J. Atmos. Chem. 1999, 33, 28-88.
[10] Westerholm, R.; Karl-Eric, E. Environ. Health Perspect. 1994, 102, 13-23.
[11] Graham, B., Mayol-Bracero, O. L.; Guyon, P.; Roberts, G. C. J. Geophys. Res. 2002, 107, D20, 8047.
[12] Saxena, P.; Hildemann, L. M.; McMurry, P. H.; Seinfeld, J. H. J. Geophys. Res. 1995, 100, 18755-18770.
[13] Lee, Y. N.; Zhou, X.; Hallock, K. J. Geophys. Res. 1995, 100, 25933-25944.
[14] Li, S. M.; Banic, C. M.; Leatich, W. R.; Liu, P. S. K.; Isaac, G. A.; Zhou, X. L.; Lee, Y. N. J. Geophys. Res. 1996, 101, 29111-29121.
[15] Lee, Y. N.; Zhou, X.; Kleinman, L. I. J. Geophys. Res. 1998, 103, 22449-22462.
[16] Grosjean, D. Eviron. Sci. Technol. 1990, 24, 1428-1432.
[17] Grosjean, E.; Grojean, D. Environ. Sci. Technol. 1996, 30, 2036-2044.
[18] Wa¨ngberg, I.; Barnes, I.; Becker, K. H. Environ. Sci. Technol. 1997, 31, 2130-2135.
[19] Grosjean, E.; Grojean, D. Environ. Sci. Technol. 1997, 31, 2421-2427.
[20] Hallquist, M.; Wangberg, I.; Ljungstrom, E.; Barnes, I.; Becker, K. H. Environ. Sci Technol. 1999, 33, 553-559.
[21] Hatakeyama, S.; Izumi, K.; Fukuyama, T.; Akimoto, H. J. Geophys. Res. 1989, 20, 13013-13024.
[22] Yu, J. Z.; Jeffries, H. E. Atmospheric Environment 1997, 31, 2261-2280
[23] Edney, E. O.; Kleindienst, T. E.; Conver, T. S.; McIver, C. D.; Weathers, W. S. Atmos. Environ. 2003, 37 (28), 3947-3965.
[24]Reisen. F.; Aschmann, S. M. Environ. Sci. Technol. 2003, 37,
4664-4671
[25] Destaillats, H.; Spaulding, R. S. Environ. Sci. Technol. 2002, 36,
2227-2235
[26] Spaulding, R. S.; Frazey, P. Anal. Chem. 1999, 71, 3420-3427
[27] Matsunaga, S.; Kawamura, K. Anal. Chem. 2000, 72, 4742-4746
[28] Le Lacheur, R. M.; Sonnenberg, L. B. Environ. Sci. Technol. 1993, 27, 2745-2753.
[29] Fitzpatrick, F. A.; Wynalda, M. A.; Kalser, D. G. Anal. Chem.
1977, 49, 1032-1035.
[30] Kobayashi, K.; Tanaka, M.; Kawai, S. J. Chromatogr. 1980, 187,
413-417.
[31] Xie, Y.; Reckhow, D. A. Ozone Sci. Eng. 1992, 14, 269-275.
[32 ]Xie, Y.; Reckhow, D. A. J. Mass Spectrosc. 1997, 32, 99-102.
[33] Nambara, T.; Kigasawa, K.; Iwata, T.; Ibuki, M. J. Chromatogr.
1975, 114, 81-86.
[34] Hoffmann, G. F.; Sweetman L. J. Chromatogr. Biomed. Appl.
1987, 421, 336-343.
[35] Hoffmann, G. F.; Sweetman, L. Clin. Chim. Acta 1991, 199, 237-
242.
[36] Luo, X. P.; Yazdanpanah, M.; Bhooi, N.; Lehotay, D. C. Anal.
Biochem. 1995, 228, 294-298.
[37] Yu, J.; Flagan, R. C.; Seinfeld, J. H. Environ. Sci. Technol. 1998, 32, 2357-2370.
[38] Zhao, L.; Lee, H. K. J. Chromatogr. A 2001, 919, 381–388
[39] Lagalante, A. F.; Felter, M. A. J. Agric. Food Chem. 2004, 52, 3744-3748
[40] Tankeviciute, A.; Kazlauskas, R. Analyst, 2001, 126, 1674–1677

[41] Saraji, M. J. Chromatogr. A 2005, 1062, 15–21
[42] Psillakis, E.; Kalogerakis, N. Trends Anal. Chem. 2002, 21, 53-63.
[43] Jeannot, M. A.; Cantwell, F. F. Anal. Chem. 1997, 69, 235-239.
[44] Lopez-Blanco, M. C.; Blanco-Cid, S. J. Chromatogr. A 2003, 984, 245-252.
[45] Palit, M.; Pardasani, D. Anal. Chem. 2005, 77, 711-717.

3-5參考文獻
[1] Sogorb, M. A.; Vilanova, E. Toxicol. Lett. 2002, 128, 215-228.
[2] Raushel, F. M. Curr. Opin, Microbiol. 2002, 5, 288-295.
[3] EEC 1980, Offic. J Euro. Communities, 1980, No. L 229, 30.08, 11.
[4] Maštovsk´a, K.; Lehotay, S. J. J. Chromatogr. A 2004, 1040, 259-272.
[5] Lee, H. B.; Weng, L. D. J. Assoc. Off. Anal. Chem. 1984, 67, 789-794.
[6] Navarro-Villoslada, F.; Perez-Arribas, L.V. Anal. Chim. Acta 1999, 381, 93-102.
[7] Hernandez, F.; Beltran, J.; Lopez, F. J. Anal. Chem. 2000, 72, 2313-2322.
[8] Sarrión, M. N.; Santos, F. J. M. Rapid Commun. Mass Spectrom. 2000, 14, 2271-2281.
[9] Su, P. G.; Huang, S.D. Talanta 1999, 49, 393–402.
[10] Zuin, V. G. J. Chromatogr. A 2004, 1056, 21–26.
[11] Doong, R. A.; Liao, P. L. J. Chromatogr. A 2001, 918, 177-188.
[12] Bouaid, A.; Ramos, L. J. Chromatogr. A 2001, 939, 13-21.
[13] Beltran, J.; Lopez, F. J. Chromatogr. A 2000, 885, 389-404.
[14] Zhang, Z.; Poerschmann J. Anal. Commun. 1996, 33, 219-221.
[15] Blasco, C.; M. Fernández, J. Chromatogr. A 2004, 1030, 77-85.
[16] Wennrich, L.; Popp, P. J. AOAC Int. 2001, 84, 1194-1201.
[17] Demyttenaere, J. C. R.; Martinez, J. I. S, J. Chromatogr. A 2004,
1030, 221-232.
[18] Baltussen, E.; Sandra P. J. Microcol. Sep. 1999, 11, 737-747.
[19] He, Y.; Lee, H. K. Anal. Chem. 1997, 69, 4634-4640.
[20] Ma, M. H.; Cantwell, F. F. Anal. Chem. 1999, 71, 388-393.
[21] De Jager, L. S.; Andrews, A. R. J. J. Chromatogr. A 2001, 911,
97-105.
[22] Psillakis, E.; Kalogerakis, N. J. Chromatogr. A 2001, 907, 211-219.
[23] Carlsson, K.; Karlberg, B. Anal. Chim. Acta 2000, 415, 137-144.
[24] Theis, A.L.; Waldack, A.J. Anal. Chem. 2001, 73, 5651-5654.
[25] Shen, G.; Lee, H.K. Anal. Chem. 2002, 74, 648-654.
[26] Basheer, C.; Lee, H. K. J. Chromatogr. A 2004, 1022, 161-169.
[27] http://www.inchem.org
[28] Eisert, R.; Levsen, K. J. Am. Mass Spectrom. 1995, 6, 1119-1130.
[29] Magdic, S.; BoydBoland, A. J. Chromatogr. A 1996, 736, 219-228.
[30] Lambropoulou, D. A.; Sakkas, V. A. J . Chromatogr . A 2002, 963, 107-116.
[31] Prieto, A.; Ettiene, G. Food Additives and Contaminants, 1999, 16, 57-61
[32] Lacorte, S.; Barcelo, A. J. Chromatogr. A 1995, 712, 103-112.

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