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中文論文名稱 以固相微萃取結合氣相層析法快速偵測賽滅淨農藥之研究
英文論文名稱 A Study of Rapid Analysis for Cyromazine by the Solid-phase Microextraction / Gas Chromatography
校院名稱 淡江大學
系所名稱(中) 水資源及環境工程學系碩士班
系所名稱(英) Department of Water Resources and Environmental Engineering
學年度 93
學期 2
出版年 94
研究生中文姓名 溫洪能
研究生英文姓名 Hong-Neng Wun
電子信箱 danper0505@yahoo.com.tw
學號 692331415
學位類別 碩士
語文別 中文
口試日期 2005-06-10
論文頁數 103頁
口試委員 指導教授-許道平
委員-門立中
委員-林孟山
中文關鍵字 賽滅淨  固相微萃取  實驗設計  直交表  蕃茄 
英文關鍵字 Cyromazine  solid-phase microextraction (SPME)  design of experiment (DOE)  Orthogonal array (OA)  Tomato 
學科別分類 學科別應用科學環境工程
中文摘要 本研究之目的為經簡單處理之蔬果樣品,結合固相微萃取與氣相層析儀偵測樣品(包心葉菜類、小葉菜類、蕃茄)中賽滅淨之含量。透過直接萃取樣品再置入儀器進行分析不但能有效縮短分析時間,且能有效降低偵測極限。
農藥賽滅淨被歸類為殺蟲劑,其代謝產物蜜胺引發癌症之疑慮,偵測賽滅淨之方法包含液相層析/紫外光偵檢器以及氣相層析儀/火焰離子偵檢器,當樣品送入儀器前,必須經過適當前處理,樣品萃取前處理經常使用大量有機溶劑,處理過程更是耗時繁瑣,分析效率實不經濟,如果能將實驗分析時間有效縮短,則有助於實驗效率之提升。
經直交表實驗設計尋求最佳實驗條件,進而探討此研究方法之可行性與實際樣品分析之應用,本研究以直交表L27(38)實驗設計所得最佳實驗條件如下,萃取時間30min,萃取溫度50℃,脫附時間5min,脫附溫度250℃,攪拌速率1000rpm,pH=7,樣品體積4mL。在此操作條件下,線性範圍0~15μg/mL,最佳回歸係數0.9932,方法偵測極限0.015μg/mL,之平均回收率105.68%(添加濃度0.2~1μg/mL, n=3),相對標準偏差8.79%(n=7)。另採得真實蔬果樣品於淡水黃昏市場蔬果種類有包心菜類、小葉菜類、蕃茄(聖女品種)等三種樣品。偵測結果顯示,在蕃茄樣品發現賽滅淨農藥含量為194μg/g,且經過30天後(儲存冰箱冷藏4℃),蔬果樣品內賽滅淨農藥由194μg/g降解為41μg/g。
英文摘要 The aim of this study is to use solid phase microextraction (SPME) technique combined with gas chromatography (GC) applied to determine the cyromazine residues in food samples. In this study, the fiber in SPME coated with 85μm Polyacrylate(PA) was used to extract cryomazine in direct immerse(DI) extraction model. The direct use of SPME to extract an aqueous suspension of solid samples has been studied. The extraction parameters for optimization have also been investigated by the design of experiment method.
Cyromazine (N-cyclopropyl-1,3,5-triazine-2,4,6-triamine) is a triazine pesticide used for fly control in cattle manure, field crops, vegetables and fruits by inhibiting insect growth. The cyromazine can be hydrolysed at extreme pH or photodegraded leading to the stable heterocyclic structure melamine (1, 3,5-triazine-2,4,6-triamine).
The design of experiment (DOE) method was applied initially to use a minimum number of experiments. Orthogonal array techniques are used to investigate the simultaneous variation of several parameters and the investigation of interactions between parameters. In order to estimate the optimum levels and determine the relative magnitude of the effect of various factors. the total 27 experiments were completed. Finally, the extraction parameters of SPME-GC for optimization were as follows:adsorption time 30min;adsorption temperature 50℃;desorption time 5min;desorption temperature 250℃;stirring rate 1000rpm;pH=7;sample volume 4mL. The limit of method detection was 0.015μg/mL. and the relative standard deviation was 8.79%(n=7). It is found that the cyromazine concentration in tomatoes from local market was 194μg/g. and the Recoveries were 105.68 %( concentration range for standard addition, 0.2~1.0μg/mL, n=3). The regression coefficient and linear range of the calibration curve were 0.9932, 0~15μg/mL, respectively.
論文目次 中文摘要………………………………………………………………………..I
英文摘要……………………………………………………………………….II
目錄…………………………………………………………………………...III
表目錄………………………………………………………………………….X
圖目錄………………………………………………………………………...XI

第一章 緒論
1.1前言…………………………………………………………………….1
1.2研究緣起…………………………………………………………….1
1.2.1賽滅淨簡介……………………………………………………..2
1.2.2賽滅淨物理化學特性…………………………………………..3
1.2.3賽滅淨抑制害蟲生長機制……………………………………..3
1.2.4賽滅淨使用現況………………………………………………...3
1.2.5賽滅淨殘留限量標準…………………………………………...4
1.2.6賽滅淨施用標準………………………………………………..4
1.2.7蕃茄斑潛蠅簡介………………………………………………..4
1.2.8蕃茄斑潛蠅危害作物範圍……………………………………...5
1.3研究目的……………………………………………………………….5
1.4研究內容……………………………………………………………….6
1.5研究架構……………………………………………………………….6

第二章 文獻回顧
2.1賽滅淨偵測方法………………………………………………………8
2.1.1氣相層析法(gas chromatography, GC)………………………….8
2.1.1.1GC/FID...……………………………………………………….9
2.1.1.2GC/NPD……………………………………………………….9
2.1.1.3GC/MS…………………………………………………………9
2.1.2液相層析法(liquid chromatography, LC)………………………..9
2.1.2.1 HPLC/UV(high performance LC)…………………………...10
2.1.2.2 LC/UV………………………………………………………..10
2.1.2.3 LC-ESI/MS/MS………………………………………………10
2.1.3電生成化學發光法(electrogenerated chemiluminescence, ECL)..11
2.2三氮井化合物偵測方法……………………………………………...11
2.3固相微萃取法(solid-phase microextraction, SPME)………………...19
2.3.1固相微萃取法原理………………………………………………19
2.3.1.1直接浸入式固相微萃取法(DI-SPME)……..………………..20
2.3.1.2頂空式固相微萃取法(HS-SPME)….………………………..20
2.3.2固相微萃取模式………………………………………………….21
2.3.3固相微萃取法之影響因子……………………………………….23
2.3.3.1纖維披覆靜相膜之影響…………………………………….23
2.3.3.2樣品體積之影響…………………………………………….24
2.3.3.3吸附平衡時間之影響……………………………………….24
2.3.3.4吸附溫度之影響…………………………………………….25
2.3.3.5脫附溫度、時間之影響…………………………………….25
2.3.3.6樣品攪拌速率之影響……………………………………….26
2.3.3.7酸鹼度(pH)之影響………………………………………….26
2.4實驗設計(design of experiment, DOE)……………………………..27
2.4.1實驗設計之相關研究……………………………………………28

第三章 實驗設備及材料
3.1儀器設備……………………………………………………………..29
3.1.1氣相層析儀(gas chromatography, GC)…………………………29
3.1.1.1氣體供給設備………………………………………………..30
3.1.1.2操作條件……………………………………………………..30
3.1.1.3資料處理系統………………………………………………..31
3.1.2固相微萃取(solid-phase micro-extraction, SPME)裝置…………31
3.1.2.1固相微萃取裝置使用說明…………………………………..31
3.1.2.2固相微萃取纖維調理(conditioned)…………………………..37
3.1.3一般實驗設備……………………………………………………38
3.1.4容器之清洗………………………………………………………39
3.2實驗藥品與試劑……………………………………………………...39
3.3賽滅淨標準品及環境樣品檢液配製………..……………………….40
3.3.1賽滅淨標準品配製……………………………………………….40
3.3.2環境基質樣品檢液之調製………………………………………40
3.4實驗分析方法………………………………………………………...41
3.4.1直接浸入式固相微萃取(DI-SPME)最佳條件萃取步驟……….41
3.4.2檢量線製備……………………………………………………….45
3.4.3方法偵測極限(method detection limit, MDL)………………….46
3.4.3.1方法偵測極限預估……………………………………..........46
3.4.3.2方法偵測極限確認………………………………………….47
3.4.4方法空白試驗……………………………………………………48
3.4.5真實樣品分析……………………………………………………48
3.4.6標準添加法………………………………………………………49
3.4.7精密度試驗………………………………………………………50

第四章 實驗設計
4.1實驗設計(design of experiment)……………………………………..52
4.1.1實驗設計沿革……………………………………………………52
4.1.2實驗設計軟體-Minitab…………….…………………………53
4.2直交表(orthogonal array, OA)………………………………………..54
4.3反應曲面法(response surface methodology, RSM)………………...55
4.4實驗設計流程………………………………………………………...56
4.4.1訂定實驗目的……………………………………………………56
4.4.2提出所有實驗影響因子(特性要因圖)…………………………57
4.4.3實驗影響因子篩選………………………………………………57
4.4.3.1既定實驗因子……………………………………………….57
4.4.3.2最佳化萃取實驗因子……………………………………….60
4.4.4實驗配置………………………………………………………….63
4.4.5實驗說明………………………………………………………….63
4.4.6數據彙整…………………………………………………………66
4.4.7擬定最佳操作條件………………………………………………67
4.4.8最佳操作條件驗證………………………………………………67

第五章 結果與討論
5.1固相微萃取(SPME)/氣相層析儀(GC/FID)分析條件建立………….68
5.1.1氣相層析儀/火焰離子偵檢器(GC/FID)分析條件建立…………68
5.1.1.1賽滅淨停留時間建立………………………………………..69
5.1.2固相微萃取(SPME)最佳萃取條件建立…………………………69
5.1.2.1第一階段SPME最佳萃取條件試驗-L27(38) ……………….69
5.1.2.1.1 L27(38)實驗結果………………………………………….72
5.1.2.1.2實驗因子探討(顯著因子) ………………………………76
5.1.2.1.3實驗因子探討(重要因子)………………………..………76
5.1.2.2第二階段SPME最佳萃取條件試驗-L4(22)…………………77
5.1.2.2.1 L27(38)實驗結果………………………………………….77
5.1.2.2.2實驗因子探討……………………………………………79
5.1.3最佳化萃取條件參數…………………………………………….79
5.2檢量線…………………………………………………………………81
5.3方法偵測極限…………………………………………………………83
5.4方法空白試驗…………………………………………………………85
5.5真實樣品抽樣檢驗……………………………………………………85
5.6標準添加法……………………………………………………………86
5.7精密度試驗……………………………………………………………89

第六章 結論與建議
6.1結論…………………………………………………………………..90
6.2建議…………………………………………………………………...91

參考文獻……………………………………………………………………..92
附件………………………………………………………………………..101


表目錄

表2.1以SPME前處理萃取分析土壤樣品中Triazines之相關研究案例…13
表2.2以SPME前處理萃取分析液態樣品中Triazines之相關研究案例…15
表3.1 SPME纖維種類之特性及其應用…………………………………….35
表3.2 GC操作條件之纖維調理建議值……………………………………..37
表4.1 L9(34) 直交表………………………………………………………….55
表4.2實驗因子水準設定…………………………………………………….63
表5.1 L27(38)直交表實驗因子水準配置……………………………………71
表5.2 L27(38)直交表實驗結果………………………………………………..74
表5.3 L4(22)直交表實驗配置與結果………………………………………...78
表5.4 SPME-GC/FID賽滅淨檢量線實驗結果………………………………82
表5.5查核檢量線測試結果……………………………………….…………83
表5.6方法偵測極限測試結果……………………………………………….84
表5.7標準添加法測試結果………………………………………………….88
表5.8賽滅淨檢量線換算標準添加法之結果……………………………….88
表5.9精密度測試結果……………………………………………………….89

圖目錄

圖1.1研究架構…………….…………………………………………………..7
圖2.1浸入式、頂空式固相微萃取法示意圖………………………………..22
圖3.1手動固相微萃取裝置結構細部分解………………………………….33
圖3.2手動固相微萃取裝置完整安裝……………………………………….34
圖3.3手動固相微萃取連續循環流程……………………………………….42
圖3.4手動固相微萃取位置………………………………………………….44
圖3.5真實樣品前處理-萃取-進樣完整分析流程…………………………..51
圖4.1直交表型式…………………………………………………………….54
圖4.2特性要因圖-影響萃取與脫附效果之因素……………………………58
圖4.3直接浸入式固相微萃取水浴加熱攪拌裝置………………………….65
圖5.1實驗因子對應波峰面積之主效應圖………………………………….75
圖5.2萃取溫度與鹽類添加對應波峰面積之主效應圖……………………78
圖5.3萃取溫度與鹽類添加對波峰面積之反應曲面圖……………………80
圖5.4萃取溫度與鹽類添加對波峰面積之等高線圖……………………….80
圖5.5鹽類添加影響萃取效果層析圖……………………………………….81
圖5.6 SPME-GC/FID賽滅淨檢量線…………………………………………82
圖5.7方法空白試驗層析圖………………………………………………….85
圖5.8蕃茄樣品分析試驗層析圖…………………………………………….86
圖5.9標準添加法檢量線…………………...………………………………..88



參考文獻 1. Fagoonee, I and V Toory. “Contribution to the study of the biology and ecology of the leaf-miner liriomyza tyifolii and its control by Neem”. Insect sri. Application 1(5) (1984) 23.
2. Genung, W. G. and M.J. Janes. Host range, “Wild host significance and in-field spread of liriomyza tyifolii and population buildup and effects of its parasites in relation to fall and winter celery.” Belle Glade AREC Research Reporter 18 (1975) 25.
3. 劉達修,王玉沙,“非洲菊斑潛蠅之藥劑篩選及黃色黏板在防治上之應用”台中區農業改良場研究彙報36 (1992) 7.
4. Gang Shen, Hian Kee Lee, “Determination of triazines in soil by microwave-assisted extraction followed by solid-phase microextraction and gas chromatography–mass spectrometry”, Journal of Chromatography A 985 (2003) 167.
5. 鄭允“防制非洲菊斑潛蠅之用藥選擇”興農雜誌68 (1989) 31.
6. 賽滅淨 (Cyromazine) 農藥有效成分檢驗方法,92.1.14 行政院農業委員會農糧字第0920020073號公告
7. Barke, J., Ort, J.F. and Carter, A. T. “Effect of the insect growth regulator CGA-72662(Larvadex) on broiler breeder production, hatchability and subsequent chick performance.” Sci. 63 (1984) 910.
8. Obrien, D.J and Fahey, G. “Control of fly strike in sheep by means of a pour-on formulation of cyromazine.” Vet. Rec. 129(16) (1991) 351.
9. 行政院衛生署藥物食品檢驗局, “動物用藥殘留標準”,94.4.15衛署食字第0940403032號。
10. 行政院衛生署藥物食品檢驗局, “農產品農藥殘留容許量”,93.10.26. 衛署食字第0930414022號
11. 黃莉欣 蘇文瀛,“植物蟲害及防治概論”行政院農業委員會農業藥物毒物試驗所技術專刊第131號。
12. 行政院農業委員會中區農業改良場首頁.http://www.tdais.gov.tw/
13. John P. Toth and Promode C. Bardalaye “Capillary gas chromatographic separation and mass spectrometric detection of cyromazine and its metabolite melamine”, Journal of Chromatography A 408 (1987) 335.
14. Paolo Cabras, Marco Meloni and Lorenzo Spanedda “High-performance liquid chromatographic separation of cyromazine and its metabolite melamine”, Journal of Chromatography A 505(2) (1990) 413.
15. 繆佳紋, “電生成化學發光法在賽滅淨農藥分析上的應用”,淡江大學化學系碩士班碩士論文,民國93年6月。
16. 西田政司,“GCによる農産物中の残留農薬の多成分分析法(Ⅱ)Envi-Carb/NH2カートリッジカラム精製による有機窒素系農薬の分析”,福岡市保健環境研究所,下水道局水質管理課。
17. Robert A. Yokley, Louis C. Mayer, Ruhi Rezaaiyan, Myra E. Manuli, and Max W. Cheung, “Analytical Method for the Determination of Cyromazine and Melamine Residues in Soil Using LC-UV and GC-MSD”, J. Agric. Food Chem 48 (2000) 3352.
18. J.V. Sancho∗, M. Ib´a˜nez, S. Grimalt, O´ .J. Pozo, F. Herna´ndez, “Residue determination of cyromazine and its metabolite melamine in chard samples by ion-pair liquid chromatography coupled to electrospray tandem mass spectrometry”, Analytica Chimica Acta 530 (2005) 237.
19. 李蕙芳,“長效性殺蟲劑賽滅淨在禽畜肉品檢測法開發及其殘留量調查”,國立海洋大學食品科系碩士在職專班碩士論文,民國90年6月。
20. C.G. Zambonin, F. Catucci, F. Palmisano, “Solid phase microextraction coupled to gas chromatography-mass spectrometry for the determination of the adsorption coefficients of triazines in soil”. Analyst 123 (1998) 2825.
21. A. Bouaid, L. Ramos, M.J. Gonzalez, P. Fernandez, C. “Solid-phase microextraction method for the determination of atrazine and four organophosphorus pesticides in soil samples by gas chromatography”, J. Chromatogr. A 939 (2001) 13.
22. M. Moder, P. Popp, R. Eisert, J. Pawliszyn, Fresenius J. Anal. Chem. 363 (1999) 680.
23. F. Hernandez, J. Beltran, F.J. Lopez, J.V. Gaspar, “Use of solid-phase microextraction for the quantitative determination of herbicides in soil and water samples”, Anal. Chem. 72 (2000) 2313.
24. H. Prosen, L. Zupancic-kralj, “Solid-phase microextraction”, Acta Chim. Slov. 45 (1998) 1.
25. C.G. Zambonin, F. Palmisano, “Determination of triazines in soil leachates by solid-phase microextraction coupled to gas chromatography–mass spectrometry”. J. Chromatogr. A 874 (2000) 247.
26. C. Aguilar, S. Penalver, E. Pocurull, F. Borrull, R.M. Marce, “Solid-phase microextraction and gas chromatography with mass spectrometric detection for the determination of pesticides in aqueous samples”, J. Chromatogr. A 795 (1998) 105.
27. R. Ferrari, T. Nilsson, R. Arena, P. Arlati, G. Bartolucci, R. Basla, F. Cioni, G. Carlo, P. Dellavedova, E. Fattore, M. Fungi, C. Grote, M. Guidotti, S. Morgillo, L. Muller, M. Volante, “Inter-laboratory validation of solid-phase microextraction for the determination of triazine herbicides and their degradation products at ng/l level in water samples”, J. Chromatogr. A 795 (1998) 371.
28. R. Hu, D. Elia, J.M. Berthion, S. Poliak, “Determination of triazines and amides in water using solid phase microextraction coupled with GC-MS”, Chromatographia 53 (2001) 306.
29. T.K. Choudhury, K.O. Gerhardt, T.P. Mawhinney, “Solid-phase microextraction of nitrogen- and phosphorus-containing pesticides from water and gas chromatographic analysis”, Environ. Sci. Technol. 30 (1996) 3259.
30. A.A. Boyd-Boland, J.B. Pawliszyn, “Solid-phase microextraction of nitrogen-containing herbicides”. J. Chromatogr. A 704 (1995) 163.
31. I.J. Barnabas, J.R. Dean, I.A. Fowlis, S.P. Owen, “Automated determination of s-triazine herbicides using solid-phase microextraction”. J. Chromatogr. A 705 (1995) 305.
32. A.A. Boyd-Boland, S. Magdic, J.B. Pawliszyn, “Simultaneous determination of 60 pesticides in water using solid-phase microextraction and gas chromatography-mass spectrometry”, Analyst 121 (1996) 929.
33. J. Dugay, C. Miege, M.C. Hennion, “Effect of the various parameters governing solid-phase microextraction for the trace-determination of pesticides in water”, J. Chromatogr. A 795 (1998) 27.
34. D.A. Lambropoulou, V.A. Sakkas, D.G. Hela, T.A. Albanis, “Application of solid-phase microextraction in the monitoring of priority pesticides in the Kalamas River”, J. Chromatogr. A 963 (2002) 107.
35. A. Ramesh, P.E. Ravi, “Applications of solid-phase microextraction (SPME) in the determination of residues of certain herbicides at trace levels in environmental samples”, J. Environ. Monit. 3 (2001) 505.
36. D.A. Lambropoulou, I.K. Konstantinou, T.A. Albanis, Int. “Determination of herbicides in natural waters using solid phase microextraction (SPME) and gas chromatography coupled with flame thermionic and mass spectrometric detection”, J. Environ. Anal. Chem. 78 (2000) 223.
37. R. Eisert, K. Levsen, “Development of a prototype system for quasi-continuous analysis of organic contaminants in surface or sewage water based on in-line coupling of solid-phase microextraction to gas chromatography”, J. Chromatogr. A 737 (1996) 59.
38. S. Meredith, S. Curren, J.W. King, “New sample preparation technique for the determination of avoparcin in pressurized hot water extracts from kidney samples”, J. Agric. Food Chem. 49 (2001) 2175.
39. A. Navalon, A. Prieto, L. Araujo, J.L. Vilchez, “Determination of oxadiazon residues by headspace solid-phase microextraction and gas chromatography–mass spectrometry”, J. Chromatogr. A 946 (2002) 239.
40. M.C. Sampedro, O. Martin, C.L. de Armentia, M.A. Goicolea, E. Rodriguez, Z.G. de Balugera, J. Costa-Moreira, R.J. Barrio, “Solid-phase microextraction for the determination of systemic and non-volatile pesticides in river water using gas chromatography with nitrogen–phosphorous and electron-capture detection”, J. Chromatogr. A 893 (2000) 347.
41. A. Navalon, A. Prieto, L. Araujo, J.L. Vilchez, Chromatographia 54 (2001) 377.
42. S.H. Salleh, Y. Saito, K. Jinno, “An approach to solventless sample preparation procedure for pesticides analysis using solid phase microextraction/supercritical fluid extraction technique”, Anal. Chim. Acta 418 (2000) 69.
43. M. Vitali, M. Guidotti, R. Giovinazzo, O. Cedrone, “Determination of pesticide residues in wine by SPME and GC/MS for consumer risk assessment”, Food Addit. Contam. 15 (1998) 280.
44. Janusz Pawliszyn, “Solid Phase Microextraction Theory and Practice.” WILEY-VCH, 1998.
45. F. Guan, K. Watanabe, A. Ishii, H. Seno, T. Kumazawa, H. Hattori, O. Suzuki, “Headspace solid-phase microextraction and gas chromatographic determination of dinitroaniline herbicides in human blood, urine and environmental water”. J. Chromatogr. B 714 (1998) 205.
46. Y. Gou, R. Eisert, J. Pawliszyn, “Automated in-tube solid-phase microextraction–high-performance liquid chromatography for carbamate pesticide analysis” J. Chromatogr. A 873 (2000) 137.
47. M. Lee, R. Lee, Y. Lin, C. Chen, B. Hwang, “Gas-phase postderivatization following solid-phase microextraction for determining acidic herbicides in water ”Anal. Chem. 70 (1998) 1963.
48. T. Kumazawa, X.P. Lee, K. Kondo, K. Sato, H. Seno, K. Watanabe-Suzuki, A. Ishii, O. Suzuki, “Determination of triazine herbicides in human body fluids by solid-phase microextraction and capillary gas chromatography” Chromatographia 52 (2000) 195.
49. T. Henriksen, B. Svensmark, B. Lindhardt, R.K. Juhler, “Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC–MS” Chemosphere 44 (2001) 1531.
50. M. Takino, S. Daishima, T. Nakahara, “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 126 (2001) 602.
51. M. Natangelo, S. Tavazzi, R. Fanelli, E. Benfenati, “Analysis of some pesticides in water samples using solid-phase microextraction–gas chromatography with different mass spectrometric techniques”J. Chromatogr. A 859 (1999) 193.
52. T. Nilsson, D. Bagilo, I. Galdo-Miguez, J.O. Madsen, S. Facchetti, “Derivatisation/solid-phase microextraction followed by gas chromatography–mass spectrometry for the analysis of phenoxy acid herbicides in aqueous samples ” J. Chromatogr. A 826 (1998) 211.
53. K.N. Graham, L.P. Sarna, G.R.B. Wesbster, J.D. Gaynor, H.Y.F. Ng, “Solid-phase microextraction of the herbicide metolachlor in runoff and tile-drainage water samples” J. Chromatogr. A 725 (1996) 129.
54. C. Gonzalez-Barreiro, M. Lores, M.C. Casais, R. Cela, “Optimisation of alachlor solid-phase microextraction from water samples using experimental design” J. Chromatogr. A 896 (2000) 373.
55. L.J. Krutz, S.A. Senseman, A.S. Sciumbato, “Solid-phase microextraction for herbicide determination in environmental samples”, Journal of Chromatography A 999 (2003) 103.
56. A. Namera, T.Watanabe, M. Yashiki, Y. Iwasaki, T. Kojima, “Simple analysis of arylamide herbicides in serum using headspace-solid phase microextraction and GC/MS” Forensic Sci. Int. 103 (1999) 217.
57. Anna A. Boyd-Boland, Janusz B. Pawliszyn, “Solid-phase microextraction of nitrogen-containing herbicides”, Journal of Chromatography A 704 (1995) 163.
58. A.C. Gerecke, C. Tixier, T. Bartels, R.P. Schwarzenbach, S.R. Muller, “Determination of phenylurea herbicides in natural waters at concentrations below 1 ng l−1 using solid-phase extraction, derivatization, and solid-phase microextraction–gas chromatography–mass spectrometry” J. Chromatogr. A 930 (2001) 9.
59. H. Kataoka, H.L. Lord, J. Pawliszyn, “Applications of solid-phase microextraction in food analysis” J. Chromatogr. A 880 (2000) 35.
60. 李世彪,“實驗計劃法在碘系偏光膜延伸染色製程條件之研究”,國立台北科技大學有機高分子研究所碩士論文,民國九十二年六月。
61. 莊春南,“利用煉鋼廠電弧爐熔融處理垃圾焚化飛灰實場測試研究”,國立中山大學環境工程研究所,民國九十二年六月。
62. 行政院環境保護署環境檢驗所,“環境檢驗室檢量線製備及確認指引”,93年10月4日環署檢字第0930072069C號公告修正
63. 行政院環境保護署環境檢驗所,“環境檢驗方法偵測極限測定指引”,九十三年十月四日環署檢字第0930072069G 號公告
64. 行政院衛生署藥物食品檢驗局,“食品中殘留農藥檢驗方法-殺蟲劑依殺之檢驗”,92年7月署授食字第 0929214751號公告
65. 黎正中、陳源樹 編譯,“實驗設計與分析”,高立圖書有限公司,民國92年9月10日。
66. 丁志華、戴寶通,“田口實驗計劃法(I)”,毫微米通訊,第八卷,第三期。
67. 鐘清章 等,品質工程(田口方法),中華民國品質學會,民國八十七年九月出版二刷。
68. 吳嘉晟、鄭大興,“製造業六標準差應用手冊”,新文京開發出版有限公司,民國九十二年一月。
69. G.E.P. Box and K.B. Wilson, On the experimental attainment of optimum conditions, Journal of the Royal Statistical Society 13 (1951), 1.
70. J.J. Langenfeld, S.B. Hawthorne, D.J. Miller, “Optimizing Split/splitless Injection Port Parameters for Solid-Phase Microextraction.”, Journal of Chromatography A 740 (1996) 139.

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