§ 瀏覽學位論文書目資料
  
系統識別號 U0002-2806200513572500
DOI 10.6846/TKU.2005.00691
論文名稱(中文) 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
論文名稱(英文) A Study of Rapid Analysis for Cyromazine by the Solid-phase Microextraction / Gas Chromatography
第三語言論文名稱
校院名稱 淡江大學
系所名稱(中文) 水資源及環境工程學系碩士班
系所名稱(英文) Department of Water Resources and Environmental Engineering
外國學位學校名稱
外國學位學院名稱
外國學位研究所名稱
學年度 93
學期 2
出版年 94
研究生(中文) 溫洪能
研究生(英文) Hong-Neng Wun
學號 692331415
學位類別 碩士
語言別 繁體中文
第二語言別
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
關鍵字(中) 賽滅淨
固相微萃取
實驗設計
直交表
蕃茄
關鍵字(英) Cyromazine
solid-phase microextraction (SPME)
design of experiment (DOE)
Orthogonal array (OA)
Tomato
第三語言關鍵字
學科別分類
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.
第三語言摘要
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
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